Conductive composition vand conductive cross-linked product, capacitor and production method thereof, and antistatic coating material, antistatic coating, antistatic film, optical filter, and optical information recording medium

ABSTRACT

A conductive composition comprises a π conjugated conductive polymer, a dopant, and a nitrogen-containing aromatic cyclic compound. A capacitor comprises an anode composed of a porous material of valve metal, a dielectric layer formed by oxidizing the surface of the anode, and a cathode provided on the dielectric layer and having a solid electrolyte layer containing a π conjugated conductive polymer, which comprises an electron donor compound containing an electron donor element provided between the dielectric layer and the cathode. Another capacitor is based on the above-described capacitor, wherein the solid electrolyte layer further comprises a dopant and a nitrogen-containing aromatic cyclic compound. An antistatic coating material comprises a π conjugated conductive polymer, a solubilizing polymer containing an anion group and/or an electron attractive group, a nitrogen-containing aromatic cyclic compound, and a solvent. An antistatic coating is formed by applying the antistatic coating material.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.11/211,557 filed Aug. 25, 2005, which claims priority on Japanese PatentApplication No. 2004-249993, filed on Aug. 30, 2004, Japanese PatentApplication No. 2004-249994, filed on Aug. 30, 2004, Japanese PatentApplication No. 2004-277168, filed on Sep. 24, 2004, Japanese PatentApplication No. 2005-090322, filed on Mar. 28, 2005, Japanese PatentApplication No. 2005-090323, filed on Mar. 28, 2005, Japanese PatentApplication No. 2005-096599, filed on Mar. 30, 2005, and Japanese PatentApplication No. 2005-108539, filed on Apr. 5, 2005, the contents ofwhich are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a conductive compound and a conductivecross-linked product, both containing a π conjugated conductive polymer.The present invention further relates to capacitors such as aluminum,tantalum, and niobium electrolytic capacitors and a production methodthereof. The present invention further relates to an antistatic coatingmaterial for imparting antistatic properties to films, an antistaticcoating having antistatic properties, an antistatic film used forwrapping food products and electronic parts, an optical filter used forthe front surface of liquid crystal displays and plasma displays, and anoptical information recording medium such as CDs and DVDs.

2. Description of Related Art

Generally, π conjugated conductive polymers composed of the main chainof a conjugated system containing π electrons are synthesized byelectrolytic polymerization or chemical oxidative polymerization.

In the electrolytic polymerization, a previously prepared base such asan electrode material is immersed in a mixed solution of an electrolyteas a dopant and precursor monomers for constituting a π conjugatedconductive polymer to form a film of π conjugated conductive polymer onthe base. Therefore, mass production is very difficult.

On the other hand, there are no such limitations on the chemicaloxidative polymerization. A large amount of a π conjugated conductivepolymer can be produced in a solution by adding oxidant and oxidationpolymerization catalysis to precursor monomers of the it conjugatedconductive polymer.

However, the π conjugated conductive polymer is obtained as an insolublesolid power in the chemical oxidative polymerization because the polymerbecomes less soluble in a solvent as the conjugated system of the mainchain of the polymer grows. It is difficult to form a uniform film of aπ conjugated conductive polymer on a base surface if the polymer isinsoluble.

Therefore, some methods to solubilize the π conjugated conductivepolymers have been attempted. They are a method of introducing afunctional group into the polymers, a method of dispersing the polymersin a binder resin, and a method of adding an anion group-containingpolymeric acid to the polymer.

For example, a method of preparing an aqueous solution ofpoly(3,4-dialkoxythiophene) by chemical oxidative polymerization of3,4-dialkoxythiophene using oxidant in the presence of polystyrenesulfonic acid, which is an anion group-containing polymeric acid havinga molecular weight of 2000 to 500000, in order to improve thedispersibility in water, is disclosed in Japanese Patent Publication No.2636968. A method of preparing an aqueous colloid solution of a πconjugated conductive polymer by chemical oxidative polymerization of aprecursor monomer of the polymer in the presence of polyacrylic acid, isdisclosed in Japanese Unexamined Patent Application, First PublicationNo. 7-165892.

According to methods disclosed in Japanese Patent Publication No.2636968 and Japanese Unexamined Patent Application, First PublicationNo. 7-165892, an aqueous dispersion solution containing a π conjugatedconductive polymer can be easily prepared. These methods require a πconjugated conductive polymer to contain a large amount of aniongroup-containing polymeric acid for ensuring its dispersibility.Therefore, the problem occurs that the obtained conductive compositionscontain a large amount of compounds which do not contribute toconductivity, making it difficult to achieve high conductivity.

In the chemical oxidative polymerization, high oxidative oxidants causeunfavorable side reactions in high probability during chemical oxidativepolymerization. Therefore, the polymer structures having poor conjugatedproperty may be produced, or the produced polymer may be attacked by theoxidant once again and excessively oxidized, and then the obtained πconjugated conductive polymer has low conductivity. Some methods areused to solve these problems, such as using transition metal ions ascatalysis or allowing reaction at a low temperature for a long time.However, these methods fail to sufficiently prevent conductivity fromdropping because the produced polymer is attacked by protons produced bydehydrogenation of reactive monomers, and, therefore, the π conjugatedconductive polymer may have low structural regularity.

Furthermore, when the conductive composition contains a binder resin, aπ conjugated conductive polymer obtained by the chemical oxidativepolymerization may have low compatibility with the binder resin.

As an example, π conjugated conductive polymers are used in capacitors.

Along with recent digitalized electronic devices, capacitors used inthose electronic devices are required to reduce impedance in highfrequency range. In order to meet this requirement, conventionally, acapacitor comprising a dielectric which is an oxide film of valve metalssuch as aluminum, tantalum, and niobium, and a cathode comprising a πconjugated conductive polymer formed on the surface of the oxide film.

A capacitor generally comprises an anode consisting of a porous materialof valve metal, a dielectric layer formed by oxidizing the surface ofthe anode, and a cathode formed by laminating a solid electrolyte layer,a carbon layer, and a silver layer on the dielectric layer, as shown inJapanese Unexamined Patent Application, First Publication No.2003-37024. The solid electrolyte layer of a capacitor is composed of aπ conjugated conductive polymer such as pyrrole or thiophene. The solidelectrolyte layer penetrates into the porous material, and theelectrolyte is in contact with the dielectric layer in a larger area forhigher electrostatic capacity and restores defective parts of thedielectric layer for preventing current leakage.

Known methods of forming a π conjugated conductive polymer includeelectrolytic polymerization (Japanese Unexamined Patent Application,First Publication No. 63-158829) and chemical oxidative polymerization(Japanese Unexamined Patent Application, First Publication No.63-173313).

In electrolytic polymerization, a conductive layer of manganese oxidemust be previously formed on the porous material surface of the valvemetal. This method is complicated and troublesome, and further manganeseoxide has low conductivity and then the effect of using a highconductive π conjugated conductive polymer is impaired.

The chemical oxidative polymerization requires a long polymerizationtime. It also requires repeated polymerization to ensure thickness.Therefore, the capacitor suffers from low production efficiency and lowconductivity.

Furthermore, a method that eliminates the step of forming a conductivepolymer on a dielectric layer in the electrolytic polymerization orchemical oxidative polymerization is proposed in Japanese UnexaminedPatent Application, First Publication No. 7-105718. Japanese UnexaminedPatent Application, First Publication No. 7-105718 describes a method inwhich aniline is polymerized in the presence of a polymeric acidcontaining a sulfo group and carboxy group to prepare water-solublepolyaniline and the polyaniline aqueous solution is applied to thedielectric layer and dried. This method is simple. However, thepolyaniline solution does not sufficiently penetrate into the porousmaterial and a polymeric acid used along with a π conjugated conductivepolymer leads to low conductivity, which, in some cases, may betemperature dependent because of the polymeric acid.

Capacitors are desired to have low equivalent series resistance (ESR),which is an index for impedance. To decrease ESR, conductivity of thesolid electrolyte layer should be increased. Highly sophisticatedcontrol over conditions of the chemical oxidative polymerization isproposed to improve the conductivity of a solid electrolyte layer inJapanese Unexamined Patent Application, First Publication No. 11-74157.However, the proposed method may further complicate complicated andtroublesome chemical oxidative polymerization, failing to simplify theprocess and reduce costs.

In some cases, π conjugated conductive polymers are used as an organicmaterial which has a conductive mechanism of electronic conduction.

Resin films themselves are insulators and easily electrically charged.Furthermore, resin films tend to charge static electricity by frictionor the like. Moreover, static electricity is not easily removed, butrather accumulates causing various problems.

Particularly, when resin films are used for wrapping food materials, inwhich sanitary considerations are emphasized, they may absorb dirt anddust and become largely deteriorated in appearance while on the shelves,which reduces the product's value. When resin films are used forwrapping powders, they absorb or repel powder that is charged whilebeing wrapped or in use, making it inconvenient and difficult to handlethe powder. When resin films are used for wrapping precision electronicdevices, the precision electronic device may be broken due to staticelectricity. Therefore, steps must be taken to assure that staticelectricity does not occur.

Optical filters and optical information recording media are requiredthat surfaces thereof are highly hard and transparent, and furthercomprise antistatic property for preventing adhesion of dust with staticelectricity. Particularly, the antistatic properties are required that asurface resistance value is stably within approximately 106 to 1010Ω(namely, stable antistatic properties). Therefore, an antistatic coatinghaving antistatic and highly hard is provided on the surfaces of opticalfilters and optical information recording media.

For imparting antistatic properties, for example, a method that a resinfilm or surfactant is applied to the surface, or a method that asurfactant is mixed into a resin film or a resin composing an antistaticcoating have been adopted (for example, see “Fine Chemical AntistaticAgents Latest Market Trend (the first volume),” Vol. 16, No. 15, 1987,p. 24-36, published by CMC).

However, since antistatic properties obtained by surfactants have aconductive mechanism of ion conduction, the surfactants are largelyinfluenced by humidity, and, therefore, optical filters and opticalinformation recording media are highly conductive at high humidity andpoorly conductive at low humidity. Hence, the antistatic function isimpaired and the antistatic ability is not exerted at need at lowhumidity and, particularly, under circumstances where static electricityeasily occurs.

If metals and carbon having a conductive mechanism of electronicconduction are used, humidity-dependence is eliminated. However, sincethey do not have transparency, they are useless where transparency isrequired.

Metal oxides such as ITO (Indium Tin Oxide) have transparency and have aconductive mechanism of electronic conduction. Therefore, metal oxidesare suitably used in transparency. However, if metal oxides are used, itis necessary to include a process using a sputtering apparatus or thelike for making a film, so that processes are complicated and productioncosts become high. Furthermore, since inorganic metal oxide coatingshave less flexibility, if the inorganic metal oxide is coated on a thinfilm base, the coating is extremely subject to cracks and does notexhibit conductivity. Moreover, since they have low adhesion property toan organic base, the inorganic metal oxide may be peeled off the organicbase at the interface thereof and transparency may be decreased.

Known organic materials having a conductive mechanism of electronicconduction include π conjugated conductive polymers. Generally, πconjugated conductive polymers are insoluble and non-melting. Therefore,it is difficult to apply them to a film base after polymerization, andan attempt is made in which aniline is polymerized in the presence of apolymeric acid having a sulfo group to form a water-soluble polyanilineand the obtained mixture is applied to a film base and dried (forexample, see Japanese Unexamined Patent Application, First PublicationNo. 1-254764).

An antistatic coating can be formed by directly polymerizing it on abase as in the method described in Japanese Unexamined PatentApplication, First Publication No. 1-25476. In such a case, theantistatic coating has a low conductivity and shows poor adhesion toresin base due to water solubility, and further, the production processbecomes more complicated.

SUMMARY OF THE INVENTION

In order to solve the aforementioned problems, the first object of thepresent invention is to provide a conductive compound and a conductivecross-linked product, both having excellent conductivity. The secondobject of the present invention is to provide a capacitor comprising acathode having a highly conductive solid electrolyte layer and lowimpedance and a method of producing the capacitor in a simple manner.The third object of the present invention is to provide an antistaticcoating material which forms an antistatic coating having highlyconductivity, flexibility, and adhesion properties to a base by simpleapplication; an antistatic coating having highly conductivity,flexibility, and adhesion properties to a base, produced by applicationas a simple production method; and an antistatic film, an opticalfilter, and an optical information recording medium, all havingexcellent antistatic properties.

The conductive composition of the present invention comprises a πconjugated conductive polymer, a dopant, and a nitrogen-containingaromatic cyclic compound

In the conductive composition of the present invention, the dopant maybe an organic sulfonic acid in the conductive composition of the presentinvention.

The organic sulfonic acid may be a sulfo group-containing solubilizingpolymer.

In the conductive composition of the present invention, thenitrogen-containing aromatic cyclic compound may be a cation of anitrogen-containing aromatic cyclic compound having a substituent bondedto the nitrogen atom.

In the conductive composition of the present invention, thenitrogen-containing aromatic cyclic compound may be substituted orun-substituted imidazoles.

Alternatively, the nitrogen-containing aromatic cyclic compound may besubstituted or un-substituted pyridines.

The capacitor of the present invention comprises an anode composed of aporous material of valve metal, a dielectric layer formed by oxidizing asurface of the anode, and a cathode provided on the dielectric layer andcomprising a solid electrolyte layer containing a π conjugatedconductive polymer, which comprises an electron donor compound layercontaining an electron donor element provided between the dielectriclayer and the cathode.

In the capacitor of the present invention, the electron donor element ofthe electron donor compound layer may be at least one element selectedfrom the group consisting of nitrogen, oxygen, sulfur, and phosphorus.

The electron donor compound of the electron donor compound layer may beat least one compound selected from the group consisting of pyrroles,thiophenes, and furans.

The electron donor compound of the electron donor compound layer may beamines.

The method of producing a capacitor of the present invention, comprisesthe steps of: a first step of oxidizing a surface of an anode composedof a porous material of valve metal and forming a dielectric layer; asecond step of applying an electron donor compound containing anelectron donor element to a surface of the dielectric layer and formingan electron donor compound layer; and a third step of forming a solidelectrolyte layer containing a π conjugated conductive polymer on asurface of the electron donor compound layer.

In the method of producing a capacitor of the present invention, thethird step may comprise a step of applying a conductive polymer solutioncontaining a π conjugated conductive polymer to the surface of theelectron donor compound layer.

Another capacitor of the present invention comprises an anode composedof a porous material of valve metal, a dielectric layer formed byoxidizing a surface of the anode, and a cathode provided on thedielectric layer, wherein the cathode comprises a solid electrolytelayer containing a π conjugated conductive polymer, a dopant, and anitrogen-containing aromatic cyclic compound.

In the capacitor of the present invention, the cathode may furthercomprise an electrolytic solution.

The dopant may be a solubilizing polymer containing an anion group.

The nitrogen-containing aromatic cyclic compound may be substituted orun-substituted imidazoles, or substituted or un-substituted pyridines.

The nitrogen-containing aromatic cyclic compound in the solidelectrolyte layer of the cathode may be cross-linked.

Another method of producing a capacitor of the present invention,comprising a step of applying a conductive polymer solution containing aπ conjugated conductive polymer, a dopant, a nitrogen-containingaromatic cyclic compound, and a solvent to a surface of a dielectriclayer of a capacitor intermediate comprising an anode composed of aporous material of valve metal and the dielectric layer formed byoxidizing a surface of the anode, and forming a coating.

In the method of producing a capacitor of the present invention, thenitrogen-containing aromatic cyclic compound in the conductive polymersolution comprises a cross-linkable functional group.

In the above case, the conductive polymer solution may further comprisea cross-linkable compound.

When the nitrogen-containing aromatic cyclic compound comprises across-linkable functional group, the method may comprise a step ofheating or irradiation with ultraviolet ray the coating after the stepof applying the conductive polymer solution and forming the coating.

The antistatic coating material of the present invention comprises a πconjugated conductive polymer, a solubilizing polymer containing ananion group and/or an electron attractive group, a nitrogen-containingaromatic cyclic compound, and a solvent.

The antistatic coating material of the present invention may furthercomprise a dopant.

The antistatic coating material of the present invention may furthercomprise a binder resin.

When the antistatic coating material of the present invention comprisesa binder resin, the binder resin may be at least one selected from thegroup consisting of polyurethane, polyester, acrylic resin, polyamide,polyimide, epoxy resin, and polyimide silicone.

The antistatic coating of the present invention is formed by applyingthe aforementioned antistatic coating material.

The antistatic film of the present invention comprises a base film andthe aforementioned antistatic coating provided on at least one surfaceof the base film.

The optical filter of the present invention comprises the aforementionedantistatic coating.

The optical information recording medium of the present inventioncomprises the aforementioned antistatic coating.

The conductive composition of the present invention has highlyconductivity (electric conductivity) and has excellent heat resistanceand moisture resistance.

When the dopant is an organic sulfonic acid, particularly, sulfogroup-containing solubilizing polymer, dispersibility in andcompatibility with a binder resin are increased.

When the nitrogen-containing aromatic cyclic compound is a cation of anitrogen-containing aromatic cyclic compound that is formed by bonding asubstituent to the nitrogen atom, it is more easily bonded orcoordinated to a dopant.

When the nitrogen-containing aromatic cyclic compound is substituted orun-substituted imidazoles or substituted or un-substituted pyridines,excellent solvent solubility is exhibited.

It is preferred in the conductive compound that the nitrogen-containingaromatic cyclic compound has a cross-linkable functional group.

In the above case, it is preferred that the conductive composition ofthe present invention further contains a cross-linkable compound.

The conductive cross-linked product of the present invention is formedby heating and/or irradiating with ultraviolet ray a conductivecomposition containing a nitrogen-containing aromatic cyclic compoundhaving a cross-linkable functional group.

In the capacitor of the present invention, the cathode has highconductivity and equivalent series resistance is low.

When the cathode comprises an electrolyte solution in the capacitor ofthe present invention, the electrostatic capacity is efficientlyderived.

When the dopant is an anion group-containing solubilizing polymer, the πconjugated conductive polymer can be high solvent solubility.

When the nitrogen-containing aromatic cyclic compound is substituted orun-substituted imidazoles or substituted or un-substituted pyridines,the π conjugated conductive polymer can be high solvent solubility.

According to the method of producing a capacitor of the presentinvention, a capacitor comprising a cathode having high conductivity andlow equivalent series resistance is produced in a simple manner.

The antistatic coating material of the present invention forms anantistatic coating having highly conductivity, flexibility, and adhesionproperties to a base by simple application. Since this antistaticcoating material realizes sufficient antistatic properties in smallamounts, the antistatic coating can be produced at low cost.

When the antistatic coating material of the present invention furthercomprises a dopant, conductivity and heat resistance of an antistaticcoating can be improved.

When the antistatic coating material of the present invention furthercomprises a binder resin, adhesion properties of the antistatic coatingcan be improved.

Particularly, when the binder resin is at least one selected from thegroup consisting of polyurethane, polyester, acrylic resin, polyamide,polyimide, epoxy resin, and polyimide silicone, it is easily mixed withthe essential components of the antistatic coating material.

The antistatic coating of the present invention has highly conductivity,flexibility, and adhesion properties to a base, and is produced byapplication as a simple production method

The antistatic film, optical filter, and optical information recordingmedium of the present invention have excellent antistatic properties,and static electricity cannot occur in them.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view showing an embodiment of the capacitoraccording to the present invention.

FIG. 2 is a cross-sectional view showing an embodiment of the opticalfilter according to the present invention.

FIG. 3 is a cross-sectional view showing an embodiment of the opticalinformation recording medium according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION π Conjugated Conductive Polymer

The π conjugated conductive polymer of the present invention can be anyorganic polymer having the main chain consisting of a π conjugatedsystem. Examples of the polymer include polypyrroles, polythiophenes,polyacetylenes, polyphenylenes, polyphenylenevinylenes, polyanilines,polyacenes, polythiophenevinylenes, and copolymers thereof.Polypyrroles, polythiophenes, and polyanilines are preferred in view ofstability in the air.

The π conjugated conductive polymer may have sufficient conductivity andcompatibility with a binder resin, even if the polymer isun-substituted. However, it is preferable to introduce a functionalgroup such as alkyl, carboxy, sulfo, alkoxy, and hydroxy groups in the πconjugated conductive polymer for improved conductibility andcompatibility.

Examples of the π conjugated conductive polymer specifically includepolypyrrole, poly(N-methylpyrrole), poly(3-methylpyrrole),poly(3-ethylpyrrole), poly(3-n-propylpyrrole), poly(3-butylpyrrole),poly(3-octylpyrrole), poly(3-decylpyrrole), poly(3-dodecylpyrrole),poly(3,4-dimethylpyrrole), poly(3,4-dibutylpyrrole),poly(3-carboxypyrrole), poly(3-methyl-4-carboxypyrrole),poly(3-methyl-4-carboxyethylpyrrole),poly(3-methyl-4-carboxybutylpyrrole), poly(3-hydroxypyrrole),poly(3-methoxypyrrole), poly(3-ethoxypyrrole), poly(3-butoxypyrrole),poly(3-methyl-4-hexyloxypyrrole), poly(thiophene),poly(3-methylthiophene), poly(3-ethylthiophene),poly(3-propylthiophene), poly(3-butylthiophene), poly(3-hexylthiophene),poly(3-heptylthiophene), poly(3-octylthiophene), poly(3-decylthiophene),poly(3-dodecylthiophene), poly(3-octadecylthiophene),poly(3-bromothiophene), poly(3-chlorothiophene), poly(3-iodothiophene),poly(3-cyanothiophene), poly(3-phenylthiophene),poly(3,4-dimethylthiophene), poly(3,4-dibutylthiophene),poly(3-hydroxythiophene), poly(3-methoxythiophene),poly(3-ethoxythiophene), poly(3-butoxythiophene),poly(hexyloxythiophene), poly(3-heptyloxythiophene),poly(3-octyloxythiophene), poly(3-decyloxythiophene),poly(3-dodecyloxythiophene), poly(3-octadecyloxythiophene),poly(3-methyl-4-methoxythiophene), poly(3,4-ethylenedioxythiophene),poly(3-methyl-4-ethoxythiophene), poly(3-carboxythiophene),poly(3-methyl-4-carboxythiophene),poly(3-methyl-4-carboxyethylthiophene),poly(3-methyl-4-carboxybutylthiophene), polyaniline,poly(2-methylaniline), poly(3-isobutylaniline), poly(2-anilinesulfonicacid), and poly(3-anilinesulfonic acid).

Among these, a (co)polymer composed of one or two compounds selectedfrom polypyrrole, polythiophene, poly(N-methylpyrrole),poly(3-methylthiophene), poly(3-methoxythiophene), andpoly(3,4-ethylenedioxythiophene) are preferably used in view of smallresistance value and high reactivity. Furthermore, polypyrrole andpoly(3,4-ethylenedioxythiophene) are more preferred because they havehigh conductivity and improve heat resistance.

The π conjugated conductive polymer comprising an alkyl group having acarbon number of 6 or larger in the substituent is preferred because itgives solvent solubility without using anion group-containingsolubilizing polymers described later. The π conjugated conductivepolymer containing an anion group as a substituent in the molecule ispreferred because the polymer itself is water-soluble.

The aforementioned π conjugated conductive polymer can be easilyobtained by chemical oxidative polymerizing precursor monomers of a πconjugated conductive polymer in a solvent in the presence of oxidant oroxidation polymerization catalysis.

Pyrroles and their derivatives, thiophenes and their derivatives, andanilines and their derivatives can be used as precursor monomers of a πconjugated conductive polymer.

Any oxidant can be used as long as it oxidizes the precursor monomers toobtain a π conjugated conductive polymer. Examples of the oxidantinclude peroxodisulfate such as ammonium peroxodisulfate, sodiumperoxodisulfate, and potassium peroxodisulfate; transition metalcompounds such as iron (II) chloride, iron (II) sulfate, iron (II)nitride, and copper (II) chloride; metal halogen compounds such as borontrifluoride and aluminum chloride; metal oxides such as silver oxide andcesium oxide; peroxides such as hydrogen peroxide and ozone; organicperoxides such as benzoyl peroxide; and oxygen.

The solvent for chemical oxidative polymerization is not limited. Anysolvent can be used as long as it dissolves or disperses the precursormonomers and maintains the oxidation ability of oxidant and oxidationcatalysis. Examples of the solvent include polar solvents such as water,N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide,dimethylsulfoxide, hexamethylenephosphortriamide, acetonitrile, andbenzonitrile; phenols such as cresol, phenol, and xylenol; alcohols suchas methanol, ethanol, propanol and butanol; ketones such as acetone andmethylethylketone; hydrocarbons such as hexane, benzene, and toluene;carboxylic acid such as formic acid and acetic acid; carbonate compoundssuch as ethylene carbonate and propylene carbonate; ether compounds suchas dioxane and diethylether; chain ethers such as ethylene glycoldialkylether, propylene glycol dialkylether, polyethylene glycoldialkylether, and polypropylene glycol dialkylether; heterocycliccompounds such as 3-methyl-2-oxazolidinone; and nitrile compounds suchas acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile,and benzonitrile. These solvents can be used individually or incombination of two or more, or mixed with other organic solvents.

(Dopant)

Any dopant may be used as long as it can change the oxidation-reductionpotential of a conjugate electron in the π conjugated conductive polymerwhile the π conjugated conductive polymer is doped/undoped. The dopantmay be a donor or an acceptor.

[Donor Dopant]

Examples of the donor dopant include alkaline metals such as sodium andpotassium; alkaline-earth metals such as calcium and magnesium; andquaternary amine compounds such as tetramethylammonium,tetraethylammonium, tetrapropylammonium, tetrabutylammonium,methyltriethylammonium, and dimethyldiethylammonium.

[Acceptor Dopant]

Examples of the acceptor dopant include halogen compounds, Lewis acids,protonic acids, organic cyano compounds, and organic metal compounds.

Examples of halogen compounds include chlorine (Cl2), bromine (Br2),Iodine (I2), iodine chloride (ICl), iodine bromide (IBr), and iodinefluoride (IF).

Examples of Lewis acids include PF5, AsF5, SbF5, BF5, BCl5, BBr5, andSO3.

Examples of organic cyano compounds include compounds containing two ormore cyano groups in the conjugated bond such as tetracyanoethylene,tetracyanoethyleneoxide, tetracyanobenzene, dichlorodicyanobenzoquinone(DDQ), tetracyanoquinodimethane, and tetracyanoazanaphthalene.

The protonic acid includes inorganic and organic acids. Examples ofinorganic acids include hydrochloric acid, sulfuric acid, nitric acid,phosphoric acid, borohydrofluoric acid, hydrofluoric acid, andperchloric acid. Examples of organic acids include organic carboxylicacid, phenols, and organic sulfonic acid.

The organic carboxylic acid may be those having one or more carboxygroups in the aliphatic, aromatic, or cyclic aliphatic series. Examplesof organic carboxylic acid include formic acid, acetic acid, oxalicacid, benzoic acid, phthalic acid, maleic acid, fumaric acid, malonicacid, tartaric acid, citric acid, lactic acid, succinic acid,monochloroacetic acid, dichloroacetic acid, trichloroacetic acid,trifluoroacetic acid, nitroacetic acid, and triphenylacetic acid.

The organic sulfonic acid may be those having one or more sulfo groupsin the aliphatic, aromatic, or cyclic aliphatic series. Examples ofthose having a sulfo group include methanesulfonic acid, ethanesulfonicacid, 1-propanesulfonic acid, 1-butanesulfonic acid, 1-hexanesulfonicacid, 1-heptanesulfonic acid, 1-octanesulfonic acid, 1-nonanesulfonicacid, 1-decanesulfonic acid, 1-dodecanesulfonic acid,1-tetradecanesulfonic acid, 1-pentadecanesulfonic acid,2-bromoethanesulfonic acid, 3-chloro-2-hydroxypropanesulfonic acid,trifluoromethanesulfonic acid, colistinmethanesulfonic acid,2-acrylamide-2-methylpropanesulfonic acid, aminomethanesulfonic acid,1-amino-2-naphthol-4-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid,3-aminopropanesulfonic acid, N-cyclohexyl-3-aminopropanesulfonic acid,benzenesulfonic acid, p-toluenesulfonic acid, xylenesulfonic acid,ethylbenzenesulfonic acid, propylbenzenesulfonic acid,butylbenzenesulfonic acid, pentylbenzenesulfonic acid,hexylbenzenesulfonic acid, heptylbenzenesulfonic acid,octylbenzenesulfonic acid, nonylbenzenesulfonic acid,decylbenzenesulfonic acid, undecylbenzenesulfonic acid,dodecylbenzenesulfonic acid, pentadecylbenzenesulfonic acid,hexadecylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid,dipropylbenzenesulfonic acid, butylbenzensulfonic acid,4-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid,m-aminobenzenesulfonic acid, 4-amino-2-chlorotoluene-5-sulfonic acid,4-amino-3-methylbenzene-1-sulfonic acid,4-amino-5-methoxy-2-methylbenzenesulfonic acid,2-amino-5-methylbenzene-1-sulfonic acid,5-amino-2-methylbenzene-1-sulfonic acid,4-amino-3-methylbenzene-1-sulfonic acid,4-acetamido-3-chlorobenzenesulfonic acid, 4-chloro-3-nitrobenzensulfonicacid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid,methylnaphthalenesulfonic acid, propylnaphthalenesulfonic acid,butylnaphthalenesulfonic acid, pentylnaphtalenesulfonic acid,dimethylmaphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid,8-chloronaphthalene-1-sulfonic acid, and sulfonic acid compoundscontaining a sulfo group such as naphthalenesulfonic acid formamidecondensation polymer and melamine sulfonic acid formamide condensationpolymer.

Examples of those having two sulfo groups include ethanedisulfonic acid,butanedisulfonic acid, pentanedecandisulfonic acid, decandisulfonicacid, m-benzenedisulfonic acid, o-benzenedisulfonic acid,p-benzenedisulfonic acid, toluenedisulfonic acid, xylenedisulfonic acid,chlorobenzenedisulfonic acid, fluorobenzenedisulfonic acid,aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid,dimethylbenzenedisulfonic acid, diethylbenzenedisulfonic acid,dibutylbenzenedisulfonic acid, naphthalenedisulfonic acid,methylnaphthalenedisulfonic acid, ethylnaphthalenedisulfonic acid,dodecylnahthalenedisulfonic acid, pentadecylnaphthalenedisulfonic acid,butylnaphthalenedisulfonic acid, 2-amino-1,4-benzenedisulfonic acid,1-amino-3,8-naphthalenedisulfonic acid,3-amino-1,5-naphthalenedisulfonic acid,8-amino-1-naphthol-3,6-disulfonic acid,4-amino-5-naphthol-2,7-disulfonic acid, anthracenedisulfonic acid,butylanthracenedisulfonic acid,4-acetamido-4′-isothio-cyanatostylbene-2,2′-disulfonic acid,4-acetamido-4′-isothiocyanatostylbene-2,2′-disulfonic acid,4-acetamido-4′-maleimidylstylbene-2,2′-disulfonic acid,1-acetoxypylene-3,6,8-trisulfonic acid,7-amino-1,3,6-naphthalenetrisulfonic acid,8-aminonaphthalene-1,3,6-trisulfonic acid, and3-amino-1,5,7-naphthalenetrisulfonic acid.

Among the organic acids, solubilizing polymers containing anion groups(hereinafter, referred to anion group-containing solubilizing polymer)are preferred. The anion group-containing solubilizing polymer ispreferably used because it does not only function as a dopant but alsosatisfactory solubilizes a π conjugated conductive polymer in a solvent,which makes the polymer usable as a coating material.

The anion group-containing solubilizing polymer may be, for example,substituted or un-substituted polyalkylenes, substituted orun-substituted polyalkenylenes, substituted or un-substitutedpolyimides, substituted or un-substituted polyamides, and substituted orun-substituted polyesters. Some of these are polymers comprising aniongroup-containing units only and the others are polymers comprising aniongroup-containing units and no anion group-containing units.

Polyalkylene is a polymer repeatedly containing methylene in the mainchain.

Polyalkenylene can be a polymer having the main chain comprising unitseach containing one vinyl group. Particularly, substituted orun-substituted butenylenes are preferred because of the interactionbetween the unsaturated bond and a π conjugated conductive polymer andeasy synthesis using substituted or un-substituted butadienes as astarting material.

Examples of polyimides include those from acid anhydrides such aspyromellitic dianhydride, biphenyl tetracarboxylic dianhydride,benzophenonetetracarboxylic dianhydride,2,2,3,3-tetracarboxydiphenylether dianhydride, and2,2-[4,4′-di(dicarboxyphenyloxy)phenyl]propane dianhydride; and diaminessuch as oxydianiline, paraphenylenediamine, metaphenylenediamine, andbenzophenonediamine.

Examples of polyamides include polyamide 6, polyamide 6,6, and polyamide6,10.

Examples of the polyesters include polyethylene terephthalate andpolybutylene terephthalate.

When the aforementioned polymers have substituent, specific examples ofthe substituents are alkyl, hydroxy, carboxy, cyano, phenyl, phenol,ester, alkoxy, and carbonyl group.

The alkyl group improves solubility and dispersibility into polar ornon-polar solvents and compatibility with and dispersibility in resins.The hydroxy group facilitates the hydrogen bond to other hydrogen atoms,improving solubility in organic solvents and compatibility with,dispersibility in, and adhesion property to resins. The cyano andhydroxyphenyl groups improve compatibility with and solubility in polarresins. They also improve heat resistance. Among them, alkyl, hydroxy,ester, and cyano groups are preferable.

Example of the alkyl group include alkyl groups such as methyl, ethyl,propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, anddodecyl and cycloalkyl groups such as cyclopropyl, cyclopentyl, andcyclohexyl. Alkyl groups having a carbon number between 1 and 12 arepreferable in view of solubility in organic solvents, dispersibility inresins, and steric hindrance.

The hydroxyl group can be, for example, a hydroxy group directly bondedto the main chain of an anion group-containing solubilizing polymer, ahydroxyl group bonded to the end of an alkyl group having a carbonnumber between 1 and 7 bonded to the main chain of an aniongroup-containing solubilizing polymer, or a hydroxyl group bonded to theend of an alkenyl group having a carbon number between 2 and 7 bonded tothe main chain of an anion group-containing solubilizing polymer. Amongthem, a hydroxyl group bonded to the end of an alkyl group having acarbon number between 1 and 6 bonded to the main chain is preferable inview of compatibility with resins and solubility in solvents.

The ester group can be, for example, an alkyl ester or aromatic estergroups directly bonded to the main chain of an anion group-containingsolubilizing polymer or an alkyl ester or aromatic ester group bondedthereto via another functional group.

The cyano group can be, for example, a cyano group directly bonded tothe main chain of an anion group-containing solubilizing polymer, acyano group bonded to the end of an alkyl group having a carbon numberbetween 1 and 7 bonded to the main chain of an anion group-containingsolubilizing polymer, or a cyano group bonded to the end of an alkenylgroup having a carbon number between 2 and 7 bonded to the main chain ofan anion group-containing solubilizing polymer.

Any anion group can be contained in the anion group-containingsolubilizing polymer, and among them, monosubstituted sulfuric acidester, monosubstituted phosphoric acid ester, carboxy, and sulfo groupsare preferable in view of easy production and stability. Sulfo group isfurther preferable in view of doping effect of functional groups on theπ conjugated conductive polymer. In other words, sulfo group-containingsolubilizing polymers are further preferable anion group-containingsolubilizing polymers.

The sulfo group-containing solubilizing polymer has a sulfo group in apolymer side chain. The main chain of a solubilizing polymer can be, forexample, polyalkylene repeatedly comprising methylene or apolyalkenylene consisting of units each containing a vinyl group in themain chain. The sulfo group can be introduced by directsulfonation/sulfation using fuming sulfuric acid, sulfonation using asulfonating agent, sulfonation through sulfonic group transposition, andpolymerization of sulfo group-containing polymerizable monomers.

In the polymerization of sulfo group-containing polymerizable monomers,sulfo group-containing polymerizable monomers and, if necessary, otherno sulfo group-containing polymerizable monomers are polymerized bychemical oxidative polymerization in the presence of oxidant and/oroxidative polymerization catalysis.

Any sulfo group-containing polymerizable monomers can be used as long asthey have sulfo-substituents at appropriate positions. Examples of suchmonomers include substituted or un-substituted ethylene sulfonic acidcompounds, substituted or un-substituted styrenesulfonic acid compounds,substituted heterocyclicsulfonic acid compounds, substituted acrylamidesulfonic acid compounds, substituted or un-substitutedcyclovinylenesulfonic acid compounds, substituted or un-substitutedbutadienesulfonic acid compounds, and vinylaromaticsulfonic acidcompounds.

Examples of substituted or un-substituted ethylenesulfonic acidcompounds include vinylsulfonic acid, vinylsulfonate, allylsulfonicacid, allylsulfonate, methallylsulfonic acid, methallylsulfonate,sulfoethylmethacrylate, sulfoethylmethacrylate,4-sulfobutylmethacrylate, 4-sulfobutylmethacrylate salt,methallyloxybenzenesulfonic acid, methallyloxybenzenesulfonate salt,allyloxybenzenesulfonic acid, and allyloxybenzenesulfonate salt.

Examples of the substituted or un-substituted styrenesulfonic acidcompounds include styrenesulfonic acid, styrenesulfonate,α-methylstyrenesulfonic acid, and α-methylstyrenesulfonate.

Examples of the substituted acrylamidosulfonic acid compounds includeacrylamide-t-butyl sulfonic acid, acrylamide-t-butylsulfonate,2-acrylamide-2-methylpropanesulfonic acid, and2-acrylamide-2-methylpropanesulfonate.

Examples of the substituted or un-substituted cyclovinylenesulfonic acidcompounds include cyclobutene-3-sulfonic acid andcyclobutene-3-sulfonate.

Examples of the substituted or un-substituted butadienesulfonic acidcompounds include isoprenesulfonic acid, isoprenesulfonate,1,3-butadiene-1-sulfonic acid, 1,3-butadiene-1-sulfonate,1-methyl-1,3-butadiene-2-sulfonic acid,1-methyl-1,3-butadiene-3-sulfonate, 1-methyl-1,3-butadiene-4-sulfonicacid, and 1-methyl-1,3-butadiene-4-sulfonate.

Among them, vinylsulfonic acid, sulfoethyl methacrylate, sulfoethylmethacrylate salt, 4-sulfobutylmethacrylate, 4-sulfobutylmethacrylatesalt, styrenesulfonic acid, styrene sulfonate, isoprene sulfonic acid,and isoprene sulfonate are preferable.

The other no sulfo group-containing polymerizable monomers can besubstituted or un-substituted ethylene compounds, substituted acrylicacid compounds, substituted or un-substituted styrenes, substituted orun-substituted vinylamines, unsaturated group-containing heterocycliccompounds, substituted or un-substituted acrylamide compounds,substituted or un-substituted cyclovinylene compounds, substituted orun-substituted butadiene compounds, substituted or un-substitutedvinylaromatic compounds, substituted or un-substituted divinylbenzenecompounds, substituted vinylphenol compounds, any substitutedsilylstyrene, and any substituted phenol compounds.

Their examples specifically include ethylene, propene, 1-buten, 2-buten,1-pentene, 2-pentene, 1-hexene, 2-hexene, styrene, p-methylstyrene,p-ethylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene,p-methoxystyrene, 2-vinylnaphthalene, 6-methyl-2-vinylnaphthalene,1-vinylimidazole, vinylpyridine, vinylacetate, acrylaldehyde,acrylonitrile, N-vinyl-2-pyrrolidone, acrylamide,N,N-dimethylacrylamide, methyl acrylate, ethyl acrylate, propylacrylate, butyl acrylate, isobutyl acrylate, isooctyl acrylate,isononylbutyl acrylate, allyl acrylate, ethyl metacrylate, hydroxyethylacrylate, methoxyethyl acrylate, methoxybutyl acrylate, stearylacrylate, acrylic acid ester, acryloylmorpholine, vinylamine,N,N-dimethylvinylamine, N,N-diethylvinylamine, N,N-dibutylyinylamine,N,N-t-butylvinylamine, N,N-diphenylvinylamine, N-vinylcarbazole, vinylalcohol, vinyl chloride, vinyl fluoride, vinyl ether, cyclopropene,cyclobutene, cyclopentene, cyclohexane, cycloheptene, cyclooctene,2-methylcyclohexene, vinylphenol, 1,3-butadiene, 1-methyl-1,3-butadiene,2-methyl-1,3-butadiene, 1,4-dimethyl-1,3-butadiene,1,2-dimethyl-1,3-butadiene, 1,3-dimethyl-1,3-butadiene,1-octyl-1,3-butadiene, 2-octyl-1,3-butadiene, 1-phenyl-1,3-butadiene,2-phenyl-1,3-butadiene, 1-hydroxy-1,3-butadiene,2-hydroxy-1,3-butadiene, allyl acrylate, acrylamideallyl, divinyl ether,o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene. Among them,preferred examples include 1-butene, vinylphenol, butyl acrylate,N-vinyl-2-pyrrolidone, and 1,3-butadiene.

The same oxidant, oxidation catalysis, and solvent can be used in thepolymerization of anion group-containing polymerizable monomers as inthe polymerization of precursor monomers for constituting a π conjugatedconductive polymer.

Examples of the anion group-containing solubilizing polymer includepolyvinylsulfonic acid, polystyrenesulfonic acid, polyallylsulfonicacid, ethyl polyacrylatesulfonic acid, butyl polyacrylatesulfonic acid,polyacrylsulfonic acid, polymethacrylsulfonic acid,poly-2-acrylamide-2-methylpropanesulfonic acid, polyisoprenesulfonicacid, polystyrene carboxylic acid, poly-2-acrylamide-2-methylpropanecarboxylic acid, polyisoprenecarboxylic acid, and polyacrylic acid. Theycan be used as individually or in combination of two or more.

The dopant can be preferably used in the conductive composition in anamount of 0.1 to 10 mol, more preferably 0.5 to 7 mol, to 1 mol of a πconjugated conductive polymer. When the dopant content is less than 0.1mol, the doping effect of the dopant on the π conjugated conductivepolymer tends to be reduced, resulting in insufficient conductivity.When the dopant content is more than 10 mol, the conductive compositioncontains a smaller amount of π conjugated conductive polymer, resultingin insufficient conductivity.

The solubilizing polymer in the antistatic coating material has an aniongroup and/or an electron attractive group in the molecules andsolubilizes the π conjugated conductive polymer in a solvent. Thesolubilizing polymer also functions as a dopant.

The solubilizing polymer containing an anion group in the molecules isas mentioned above.

The solubilizing polymer containing an electron attractive group in themolecules (hereinafter, referred to the electron attractivegroup-containing solubilizing polymer) can be a polymer comprising as aunit at least one compound selected from cyano, nitro, formyl, carbonyl,and acetyl groups.

Examples of the electron attractive group-containing solubilizingpolymer include polyacrylonitrile, polymethacrylonitrile,acrylonitrile-styrene resin, acrylonitrile-butadiene resin,acrylonitrile-butadiene-styrene resin, resin obtained by cyanoethylatinghydroxyl- or amino-containing resin, polyvinylpyrrolidone, alkylatedpolyvinylpyrrolidone, and nitrocellulose.

Among these, acrylonitrile and methacrylonitrile having acyano-containing compound as a unit are preferred. The cyano group is ahighly polar group and, therefore, improves compatibility with anddispersibility in binder resin components.

Solubilizing polymer can be a copolymer such as a copolymer of two ormore of the aforementioned anion group-containing solubilizing polymerand electron attractive group-containing solubilizing polymer, acopolymer comprising units having different anion groups, and acopolymer comprising units having different electron attractive groups.

Solubilizing polymer further can be a polymer copolymerized with othervinyl compounds such as halogenated vinyl compounds, aromatic vinyland/or their derivatives, heterocyclic vinyl compounds and/or theirderivatives, aliphatic vinyl compounds and/or their derivatives, acrylcompounds, diene compounds, and maleimide compounds.

Examples of the vinyl compounds include polymerizable vinyl compoundssuch as styrene, butadiene, acrylic acid, methacrylic acid,hydroxylacrylic acid, hydroxymethacrylic acid, acrylic acid ester,methacrylic acid ester, and p-vinyltoluene. The copolymerization withthese other vinyl compounds serves to control solvent-solubility andcompatibility with binder resins.

The solubilizing polymer can contain synthetic rubber components formodifying impact resistance, antiaging agents for improving environmentresistance, antioxidant, and UV absorbents. Amine compounds asantioxidant may inhibit the action of the oxidant for polymerizing theaforementioned conductive polymer. Therefore, phenol compounds may beused as antioxidant or the antioxidant is mixed after thepolymerization.

(Nitrogen-Containing Aromatic Cyclic Compound)

The nitrogen-containing aromatic cyclic compound has an aromatic ringhaving at least one or more nitrogen atoms wherein the nitrogen atoms inthe aromatic ring are conjugated to other atoms in the aromatic ring. Tobe conjugated, the nitrogen and other atoms have an unsaturated bond orthe nitrogen atoms are adjacent to other atoms having an unsaturatedbond when the nitrogen and other atoms themselves do not have anunsaturated bond. An unshared electrons pair on the nitrogen atoms canform a pseudo-conjugation to the unsaturated bond formed between otheratoms.

It is preferred that the nitrogen-containing aromatic cyclic compound beprovided with both the nitrogen atom conjugated to another atom and thenitrogen atom adjacent to another atom having an unsaturated bond.

The nitrogen-containing aromatic cyclic compound can be, for example,pyridine having a nitrogen atom and their derivatives, imidazoles havingtwo nitrogen atoms and their derivatives, pyrimidines and theirderivatives, pyrazines and their derivatives, and triazines having threenitrogen atoms and their derivatives. Pyridines and their derivatives,imidazoles and their derivatives, and pyrimidines and their derivativesare preferred from the standpoint of solvent solubility.

The nitrogen-containing aromatic cyclic compound may or may not have asubstituent in the ring, such as alkyl, hydroxyl, carboxy, cyano,phenyl, phenol, ester, alkoxy, and carbonyl group. Thenitrogen-containing aromatic cyclic compound can be polycyclic.

Examples of the alkyl group as a substituent include alkyl groups suchas methyl, ethyl, propyl, butyl, isobutyl, t-butyl, pentyl, hexyl,octyl, decyl, and dodecyl and cycloalkyl groups such as cyclopropyl,cyclopentyl, and cyclohexyl. Among them, alkyl groups having a carbonnumber between 1 and 12 are preferred in view of solubility in organicsolvents, dispersibility in resins, and steric hindrance.

Examples of the hydroxy group include alkylenehydroxy groups suchhydroxy, methylenehydroxy, ethylenehydroxy, trimethylenehydroxy,tetramethylenehydroxy, pentamethylenehydroxy, hexamethylenehydroxy,heptamethylenehydroxy, propylenehydroxy, butylenehydroxy, andethylmethylenehydroxy and alkenylenehydroxy groups such aspropenylenehydroxy, butenylenehydroxy, and pentenylenehydroxy.

Examples of the carboxy group include alkylenecarboxy groups suchcarboxy, methylenecarboxy, ethylenecarboxy, trimethylenecarboxy,propylenecarboxy, tetramethylenecarboxy, pentamethylenecarboxy,hexamethylenecarboxy, heptamethylenecarboxy, ethylmethylenecarboxy, andphenylethylenecarboxy, and alkenylenecarboxy groups such asisoprenecarboxy, propenylenecarboxy, butenylenecarboxy, andpentenylenecarboxy.

Examples of the cyano group include alkylenecyano groups such cyano,methylenecyano, ethylenecyano, trimethylenecyano, tetramethylenecyano,pentamethylenecyano, hexamethylenecyano, heptamethylenecyano,propylenecyano, butylenecyano, and ethylmethylenecyano; andalkenylenecyano groups such as propenylenecyano, butenylenecyano, andpentenylenecyano.

Examples of the phenol group include alkylphenol groups such phenol,methylphenol, ethylphenol, and butylphenol; and alkylenephenol groupssuch methylenephenol, ethylenephenol, trimethylenephenol,tetramethylenephenol, pentamethylenephenol, and hexamethylenephenol

Examples of the phenyl group include alkylphenyl groups such phenyl,methylphenyl, butylphenyl, octylphenyl, and dimethylphenyl;alkylenephenyl groups such methylenephenyl, ethylenephenyl,trimethylenephenyl, tetramethylenephenyl, pentamethylenephenyl,hexamethylenephenyl, and heptamethylenephenyl; and alkenylenephenylgroups such as propenylphenyl, butenylenephenyl, and pentenylenephenyl.

Examples of the alkoxy group include methoxy, ethoxy, butoxy, andphenoxy.

Examples of the pyridines and their derivatives include pyridine,2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 4-ethylpyridine,2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3-cyano-5-methylpyridine,2-pyridine carboxylic acid, 6-methyl-2-pyridine carboxylic acid,2,6-pyridine-dixarboxylic acid, 4-pyridinecarboxyaldehyde,4-aminopyridine, 2,3-diaminopyridine, 2,6-diaminopyridine,2,6-diamino-4-methylpyridine, 4-hydroxypyridine, 2,6-dihydroxypyridine,6-hydroxy methyl nicotinate, 2-hydroxy-5-pyridinemethanol, 6-hydroxyethyl nicotinate, 4-pyridinemethanol, 4-pyridineethanol,2-phenylpyridine, 3-methylquinoline, 3-ethylquinoline, quinolinol,2,3-cyclopentenopyridine, 2,3-cyclohexanopyridine,1,2-di(4-pyridyl)ethane, 1,2-di(4-pyridyl)propane,2-pyridinecarboxyaldehyde, 2-pyridinecarboxylic acid,2-pyridinecarbonitrile, 2,3-pyridinedicarboxylic acid,2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid,2,6-pyridinedicarboxylic acid, and 3-pyridinesulfonic acid.

Examples of the imidazoles and their derivatives include imidazole,2-methylimidazole, 2-propylimidazole, 2-undecylimidazole,2-phenylimidazole, N-methylimidazole, 1-(2-hydroxyethyl)imidazole,2-ethyl-4-methylimidazole, 1,2-dimethylimidazole,1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole,1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole,2-phenyl-4,5-dihydroxymethylimidazole, 1-acetylimidazole,4,5-imidazoledicarboxylic acid, 4,5-imidazoledimethyldicarboxylate,benzimidazole, 2-aminobenzimidazole, 2-aminobenzimidazole-2-sulfonicacid, 2-amino-1-methylbenzimidazole, 2-hydroxybenzimidazole, and2-(2-pyridyl)benzimidazole.

Examples of the pyrimidines and their derivatives include2-amino-4-chloro-6-methylpyrimidine,2-amino-6-chloro-4-methoxypyrimidine, 2-amino-4,6-dichloropyrimidine,2-amino-4,6-dihydroxypyrimidine, 2-amino-4,6-dimethylpyrimidine,2-amino-4,6-dimethoxypyrimidine, 2-aminopyrimidine,2-amino-4-methylpyrimidine, 4,6-dihydroxypyrimidine,2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4,6-triaminopyrimidine,2,4-dimethoxypyrimidine, 2,4,5-trihydroxypyrimidine, and2,4-pyrimidinediol.

Examples of the pyrazines and their derivatives include pyrazine,2-methylpyrazine, 2,5-dimethylpyrazine, pyrazinecarboxylic acid,2,3-pyrazinedicarboxylic acid, 5-methylpyrazine carboxylic acid,pyrazineamide, 5-methylpyrazineamide, 2-cyanopyrazine, aminopyrazine,3-aminopyrazine-2-carboxylic acid, 2-ethyl-3-methylpyrazine,2-ethyl-3-methylpyrazine, 2,3-dimethylpyrazine, and2,3-dimethylpyrazine.

Examples of the triazines and their derivatives include 1,3,5-triazine,2-amino-1,3,5-triazine, 3-amino-1,2,4-triazine,2,4-diamino-6-phenyl-1,3,5-triazine, 2,4,6-triamino-1,3,5-triazine,2,4,6-tris(trifluoromethyl)-1,3,5-triazine,2,4,6-tri-2-pyridine-1,3,5-triazine,3-(2-pyridine)-5,6-bis(4-phenylsulfonic acid)-1,2,4-triazinedisodium,3-(2-pyridine)-5,6-diphenyl-1,2,4-triazine,3-(2-pyridine)-5,6-diphenyl-1,2,4-triazine-ρ,ρ′-disodiumdisulfonate, and2-hydroxy-4,6-dichloro-1,3,5-triazine.

The nitrogen atom of the nitrogen-containing aromatic cyclic compoundhas an unshared electron pair. Therefore, a substituent or a protoncoordinates or bind to the nitrogen atom. When a substituent or a protoneasily coordinates or binds to the nitrogen atom, the nitrogen atomtends to be positively charged. Because the nitrogen and another atomare conjugated, the positive charge produced by the constituent orproton coordinated or bound to the nitrogen atom is dispersed and stablypresent in the nitrogen-containing aromatic ring.

Therefore, the nitrogen-containing aromatic cyclic compound can be acation of a nitrogen-containing aromatic cyclic compound with asubstituent introduced in the nitrogen atom. Further, the cation and ananion can be combined to form a salt. The nitrogen-containing aromaticcyclic compound in the form of a salt has the same effect as thenon-cation form of the nitrogen-containing aromatic cyclic compound.

The substituent that can be introduced in the nitrogen atom of thenitrogen-containing aromatic cyclic compound can be hydrogen or alkyl,hydroxyl, carboxy, cyano, phenyl, phenol, ester, alkoxy, or carbonylgroup.

Examples of the alkyl group include alkyl groups such as methyl, ethyl,propyl, butyl, isobutyl, t-butyl, pentyl, hexyl, octyl, decyl, anddodecyl; and cycloalkyl groups such as cyclopropyl, cyclopentyl, andcyclohexyl. Among them, alkyl groups having a carbon number between 1and 12 are preferred in view of solubility in organic solvents,dispersibility in resins, and steric hindrance.

Examples of the hydroxy group include hydroxy, alkylenehydroxy groupssuch as methylenehydroxy, ethylenehydroxy, trimethylenehydroxy,tetramethylenehydroxy, pentamethylenehydroxy, hexamethylenehydroxy,heptamethylenehydroxy, propylenehydroxy, butylenehydroxy, andethylmethylenehydroxy; and alkenylenehydroxy groups such aspropenylenehydroxy, butenylenehydroxy, and pentenylenehydroxy.

Examples of the carboxy group include carboxy, alkylenecarboxy groupssuch methylenecarboxy, ethylenecarboxy, trimethylenecarboxy,propylenecarboxy, tetramethylenecarboxy, pentamethylenecarboxy,hexamethylenecarboxy, heptamethylenecarboxy, ethylmethylenecarboxy, andphenylethylenecarboxy; and alkenylenecarboxy groups such asisoprenecarboxy, propenylenecarboxy, butenylenecarboxy, andpentenylenecarboxy.

Examples of the cyano group include cyano, alkylenecyano groups such asmethylenecyano, ethylenecyano, trimethylenecyano, tetramethylenecyano,pentamethylenecyano, hexamethylenecyano, heptamethylenecyano,propylenecyano, butylenecyano, and ethylmethylenecyano; andalkenylenecyano groups such as propenylenecyano, butenylenecyano, andpentenylenecyano.

Examples of the phenol group include phenol, alkylphenol groups such asmethylphenol, ethylphenol, and butylphenol; and alkylenephenol groupssuch methylenephenol, ethylenephenol, trimethylenephenol,tetramethylenephenol, pentamethylenephenol, and hexamethylenephenol

Examples of the phenyl group include phenyl, alkylphenyl groups such asmethylphenyl, butylphenyl, octylphenyl, and dimethylphenyl;alkylenephenyl groups such methylenephenyl, ethylenephenyl,trimethylenephenyl, tetramethylenephenyl, pentamethylenephenyl,hexamethylenephenyl, heptamethylenephenyl; and alkenylenephenyl groupssuch as propenylphenyl, butenylenephenyl, and pentenylenephenyl.

Examples of the alkoxy group include methoxy, ethoxy, butoxy, andphenoxy.

Examples of anions of that form salts together with a cation of anitrogen-containing aromatic cyclic compound include halogen, sulfateion, chlorite, and organic sulfonate ions.

The aforementioned organic sulfonic acids can be used.

For example, in the antistatic coating material, part of theincorporated nitrogen-containing aromatic cyclic compound coordinates orbinds to protons or other functional groups from the dopant, beingpositively charged and becoming a cation of the nitrogen-containingaromatic cyclic compound. Therefore, the incorporatednitrogen-containing aromatic cyclic compound is present in theantistatic coating material as a mixture of a nitrogen-containingaromatic cyclic cation compound and a nitrogen-containing aromaticcyclic compound that does not coordinate or bind. Thenitrogen-containing aromatic cyclic cation compound andnitrogen-containing aromatic cyclic compound form salts together withexcessive anion groups or electron attractive groups of the dopant, areattracted to the dopant, and penetrate into the molecules of the πconjugated conductive polymer of the antistatic coating material. Thepresence of the nitrogen-containing aromatic cyclic cation compound andnitrogen-containing aromatic cyclic compound between the molecules ofthe π conjugated conductive polymer causes the hopping energy forelectric conductivity of the π conjugated conductive polymer to drop,and therefore improves the electric conductivity of the antistaticcoating material.

The nitrogen-containing aromatic cyclic compound preferably has across-linkable functional group for improved conductivity and heatresistance. A nitrogen-containing aromatic cyclic compound having across-linkable functional group is hereinafter termed the cross-linkablenitrogen-containing aromatic cyclic compound.

A cross-linkable functional group is a functional group that reacts withand links to a functional group of the same type or of a different type.

The cross-linkable functional group can bind to the nitrogen-containingaromatic cyclic compound directly or via a functional group such assubstituted or un-substituted methylene, substituted or un-substitutedethylene, and substituted or un-substituted propylene.

The cross-linkable functional group can be introduced into a nitrogenatom or a carbon atom of the nitrogen-containing aromatic cycliccompound.

The cross-linkable functional group can be, for example, vinyl, carboxy,hydroxy, amino, or ester group. Among them, the vinyl, carboxy, andhydroxy groups are preferred because they are highly reactive andcross-linkable.

Carboxy, hydroxy, amino, and ester groups are the same as theaforementioned.

The cross-linkable nitrogen-containing aromatic cyclic compound can be,for example, a pyridine having a cross-linkable functional group andtheir derivatives and imidazole having a cross-linkable functional groupand their derivatives.

Examples of the pyridines having a cross-linkable functional group andtheir derivatives include 2-vinylpyridine, 4-vinylpyridine,2-methyl-6-vinylpyridine,

5-methyl-2-vinylpyridine, 4-butenylpyridine, 4-pentenylpyridine,2-(4-pyridyl)alcohol, 4-(1-butenylpentenyl)pyridine, 2-pyridinecarboxylic acid, 4-pyridine carboxylic acid, 6-methyl-2-pyridinecarboxylic acid, 2,3-pyridine dicarboxylic acid, 2,3 pyridinedicarboxylic acid, 2,5-pyridine dicarboxylic acid, 2,6-pyridinedicarboxylic acid, 4-hydroxypyridine, 2,6-dihydroxypyridine, 6-hydroxymethyl nicotinate, 2-hydroxy-5-pyridinemethanol, 6-hydroxy ethylnicotinate, 4-pyridine methanol, 4-pyridine ethanol, and 2-pyridinecarbonitrile.

Examples of the imidazoles having a cross-linkable functional group andtheir derivatives include N-vinylimidazole, N-allylimidazole,2-methyl-4-vinylimidazole, 2-methyl-1-vinylimidazole,imidazole-4-carboxylic acid, 4,5-imidazole dicarboxylic acid,1-(2-hydroxyethyl)imidazole, 2-hydroxymethylimidazole,4-hydroxymethylimidazole, 2-butyl-4-hydroxymethylimidazole,2-methyl-4-hydroxymethylimidazole, 4-hydroxymethyl-2-methylimidazole,1-benzyl-2-hydroxybenzimidazole, methylimidazole-4-carboxylate,ethylimidazole-4-carboxylate, and 4,5-imidazole dimethyl dicarboxylate.

The nitrogen-containing aromatic cyclic compound is preferably used inan amount of 0.1 to 100 mol, more preferably 1 to 30 mol, to 1 mole ofdopant and/or solubilizing polymer. The range from 1 to 30 mol ispreferred in view of physical properties and conductivity of thecoating. When the nitrogen-containing aromatic cyclic compound is usedin an amount of less than 0.1 mol, the interaction between thenitrogen-containing aromatic cyclic compound and the dopant and πconjugated conductive polymer tends to decrease, possibly resulting ininsufficient conductivity. When the nitrogen-containing aromatic cycliccompound is used in an amount of greater than 100 mol, the content ofthe π conjugated conductive polymer is excessively low, here againpossibly resulting in insufficient conductivity.

(Cross-Linkable Compound)

The cross-linkable nitrogen-containing aromatic cyclic compoundcontained preferably contains a cross-linkable compound.

The cross-linkable compound is preferably a compound having a vinylgroup when the cross-linkable functional group is a vinyl group, and ispreferably a compound having a hydroxy or amino group when thecross-linkable functional group is a carboxy group, and is preferably acompound having a carboxy group when the cross-linkable functional groupis a hydroxy group.

With the cross-linkable compound being introduced, the cross-linkablefunctional group of the cross-linkable nitrogen-containing aromaticcyclic compound is easily cross-linked, thereby ensuring stability.

Examples of the cross-linkable compound include methyl acrylate, ethylacrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, isooctylacrylate, isononylbutyl acrylate, allyl acrylate, ethyl methacrylate,hydroxyethyl acrylate, methoxyethyl acrylate, methoxybutyl acrylate,stearyl acrylate, acryloylmorpholine, vinyl-containing compounds such asvinylamine, N,N-dimethylvinylamine, N,N-diethylvinylamine,N,N-dibutylvinylamine, N,N-t-butylvinylamine, N,N-diphenylvinylamine,N-vinylcarbazole, vinyl alcohol, vinyl chloride, vinyl fluoride, vinylether, acrylonitrile, N-vinyl-2-pyrrolidone, and acrylamide,N,N-dimethylacrylamide, carboxy-containing compounds such as carboxylicacid, phthalic acid, acrylic acid, and polyacrylic aid, andhydroxy-containing compounds such as butanol, ethylene glycol, and vinylalcohol.

(Polymerization Initiator)

When the nitrogen-containing aromatic cyclic compound has across-linkable functional group, it is preferred to add a polymerizationinitiator. The polymerization initiator can be, for example, acids,alkalis, radical generators, or oxidants. It is preferred that thepolymerization initiator be selected according to the type of thecross-linkable functional group. When the cross-linkable functionalgroup is a vinyl group, radical generators and alkalis are preferable.When the cross-linkable functional group is a carboxy or hydroxy group,acids and alkalis are preferable.

(Binder Resin)

The conductive composition may contain a binder resin for adjustingcoating properties such as coating formation, strength, and electricconductivity. The binder resin is preferably contained in view of theantistatic coating material because the coating has a harder surface andimproved damage resistance and adhesion to a base. When an antistaticcoating material contains a binder resin, an antistatic coating formedby antistatic coating material easily has a pencil hardness (JIS K 5400)of HB or harder.

The binder resin is not limited as long as it is compatible with ormixable/dispersible in the essential components of the conductivecomposition. The binder resin can be a reactive or nonreactive resin.The binder resin can be a heat-curable resin or a thermoplastic resin aslong as it is compatible with or mixable/dispersible in the antistaticcoating material. Examples of the binder resin include polyester resinsuch as polyethylene phthalate, polybutylene phthalate, and polyethylenenaphthalate; polyimide resin such as polyimide and polyamideimide;polyamide resin such as polyamide 6, polyamide 6,6, polyamide 12, andpolyamide 11; fluorine resin such as polyvinylidene fluoride, polyvinylfluoride, polytetrafluoroethylene, ethylenetetrafluoroethylenecopolymer, and polychlorotrifluoroethylene; vinyl resin such aspolyvinyl alcohol, polyvinylether, polyvinyl butyral, polyvinyl acetate,and polyvinyl chloride; epoxy resin; xylene resin; aramide resin;polyurethane resin; polyurea resin; melamine resin; phenol resin;polyether; and acrylic resin and their copolymers.

The binder resin used in the antistatic coating material can bedissolved in an organic solvent or in water with a functional group suchas a sulfo or carboxy group being added, or dispersed in water to forman emulsion.

Among these, one or more binder resins are preferably selected frompolyurethane, polyester, acrylic resin, polyamide, polyimide, epoxyresin, and polyimide silicone because these are easy to mix. Acrylicresin is suitable for applications such as optical filters because ofexcellent hardness and transparence.

The acrylic resin preferably contains a heat-curable or photo-curableliquid polymer.

The heat-curable liquid polymer can be, for example, a reactive polymeror a self-cross-linkable polymer.

The reactive polymer is a polymer formed by polymerizing monomers havinga substituent such as carboxy group, acid anhydride, oxetanes, glycidylgroup, and amino group. Examples of the monomers include carboxylic acidcompounds such as malonic acid, succinic acid, glutamic acid, pimelicacid, ascorbic acid, phthalic acid, acetylsalicylic acid, adipic acid,isophthalic acid, benzoic acid, and m-toluic acid, acid anhydrides suchas maleic acid anhydride, phthalic acid anhydride, dodecylsuccinic acidanhydride, dichloromaleic acid anhydride, tetrachlorophthalic acidanhydride, and pyromellitic acid anhydride, oxetane compounds such as3,3-dimethyloxetane, 3,3-dichloromethyloxetane,3-methyl-3-hydroxymethyloxetane, and azidomethylmethyloxetane, glycidylether compounds such as bisphenol A diglycidyl ether, bisphenol Fdiglycidyl ether, phenolnovolacpolyglycidyl ether,N,N-diglycidyl-p-aminophenolglycidyl ether, tetrabromobisphenol Adiglycidyl ether, hydrogenerated bisphenol A diglycidyl ether (namely,2,2-bis(4-glycidyloxycyclohexyl)propane), glycidyl amine compounds suchas N,N-diglycidylaniline, tetradiglycidyldiaminodiphenylmethane,N,N,N,N-tetraglycidyl-m-xylylenediamine, triglycidylisocyanurate, andN,N-diglycidyl-5,5-dialkylhydantoin, amine compounds such asdiethylenetriamine, triethylenetetramine, dimethylaminopropylamine,N-aminoethylpiperazine, benzyldimethylamine,tris(dimethylaminomethyl)phenol, DHP30-tri(2-ethylhexoate),metaphenylenediamine, diaminophenylmethane, diaminodiphenylsulfone,dicyandiamide, boron trifluoride, monoethylamine, menthanediamine,xylenediamine, and ethylmethylimidazole, and glycidyl compounds frombisphenol A epichlorohydrin among compounds having two or more oxiranerings per molecule, and their analogs.

A cross-linker having at least two or more functional groups is used forthe reactive polymerization. The cross-linker can be, for example,melamine resin, epoxy resin, or metal oxide. As for the metal oxide,basic metal compounds such as Al(OH)₃, Al(OOC.CH3) 2(OOCH),Al(OOC.CH3)2, ZrO(OCH3), Mg(OOC.CH3), Ca(OH)2, and Ba(OH)3 can be usedas appropriate.

The self-cross-linkable polymerization involves self-cross-linkingbetween functional groups when heated, and involve, for example,glycidyl and carboxyl groups or N-methylol and carboxy group.

The photo-curable liquid polymer may be, for example, polyester, epoxyresin, oxetane resin, polyacryl, polyurethane, polyimide, polyamide,polyamideimide, and polyimide silicone oligomers or prepolymers.

Examples of monomer units constituting a photo-curable liquid polymerinclude monofunctional and polyfunctional monomers of the following:acrylates such as bisphenol A ethyleneoxide modified diacrylate,dipentaerythritolhexa(penta)acrylate,dipentaerythritolmonohydroxypentaacrylate, dipropyleneglycol diacrylate,trimethylolpropanetriacrylate, glycerinpropoxytriacrylate,4-hydroxybutylacrylate, 1,6-hexadioldiacrylate, 2-hydroxyethlacrylate,2-hydroxypropylacrylate, isobornylacrylate,polyethyleneglycoldiacrylate, pentaerythritoltriacrylate,tetrahydrofurfurylacrylate, tripropyleneglycoldiacrylate; methacrylatessuch as tetraethyleneglycol dimethacrylate, alkylmethacrylate,allylmethacrylate, 1,3-butyleneglycol dimethacrylate,n-butylmethacrylate, benzylmethacrylate, cyclohexylmethacrylate,diethyleneglycol dimethacrylate, 2-ethylhexylmethacrylate,glycidylmethacrylate, 1,6-hexanediol dimethacrylate,2-hydroxyethylmethacrylate, isobornylmethacrylate, laurylmethacrylate,phenoxyethylmethacrylate, t-butylmethacrylate,tetrahydrofurfurylmethacrylate, and trimethylolpropanetrimethacrylate;glycidyl ethers such as allylglycidyl ether, butylglycidyl ether, higheralcohol glycidyl ether, 1,6-hexanediolglycidyl ether, phenylglycidylether, and stearylglycidyl ether; acryl(methacryl) amides such asdiacetonacrylamide, N,N-dimethylacrylamide,dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide,methacrylamide, N-methylolacrylamide, N,N-dimethylacrylamide,acryloylmorpholine, N-vinylformamide, N-methylacrylamide,N-isopropylacrylamide, N-t-butylacrylamide, N-phenyl acrylamide,acryloylpiperidine, and 2-hydroxyethylacrylamide; vinyl ethers such as2-chloroethylvinyl ether, cyclohexylvinyl ether, ethylvinyl ether,hydroxybutylvinyl ether, isobutylvinyl ether, triethyleneglycol vinylether; carboxylic acid vinyl esters such as vinyl lactate, vinylmonochloroacetate, vinyl pivalate.

The photo-curable liquid polymer cures with a photopolymerizationinitiator. The photopolymerization initiator can be, for example,acetophenone, benzophenones, Michler's benzoylbenzoate, α-amyloximeester, tetramethylthiurammonosulfide, or thioxanthone. A photosensitizersuch as n-butylamine, triethylamine, and tri-n-butylphosphine can bemixed.

(Solvent)

The conductive composition may contain solvents. The aforementionedsolvents capable of dissolving or dispersing precursor monomers of a πconjugated conductive polymer may be used.

The solvent used in the antistatic coating material and capacitor is notlimited, and may be, for example, alcohol solvents such as methanol,ethanol, isopropyl alcohol (IPA); amide solvents such asN-methylpyrrolidone (NMP), and dimethylacetamide (DMAc),dimethylformamide (DMF), ketone solvents such as methylethylketone(MEK), acetone, and cyclohexane, ester solvents such as ethyl acetateand butyl acetate, toluene, xylene, and water. These can be usedindividually or in combination. Among them, in view of recentenvironmental considerations, environmental-friendly water and alcoholsolvents are preferred.

The aforementioned conductive composition can be prepared by, forexample, chemical oxidative polymerizing precursor monomers of a πconjugated conductive polymer in the presence of dopant and oxidant oroxidation polymerization catalysis and, then, adding anitrogen-containing aromatic cyclic compound thereto.

For chemical oxidative polymerizing a π conjugated conductive polymer,the dopant forms a salt together with the π conjugated conductivepolymer and the π conjugated conductive polymer is doped as it grows.Particularly, when the dopant is a sulfo group-containing solubilizingpolymer, the sulfo group aggressively forms a salt together with the πconjugated conductive polymer; therefore, the π conjugated conductivepolymer is strongly attracted to the main chain of the sulfogroup-containing solubilizing polymer dopant. Consequently, the mainchain of the π conjugated conductive polymer grows along the main chainof the sulfo group-containing solubilizing polymer dopant; thereby aregularly aligned π conjugated conductive polymer is easily formed.Forming a number of salts together with the sulfo group-containingsolubilizing polymer dopant, the π conjugated conductive polymersynthesized in this manner is anchored to the main chain of the sulfogroup-containing solubilizing polymer dopant and forms a mixture withit.

By adding a nitrogen-containing aromatic cyclic compound to the mixtureof the π conjugated conductive polymer and dopant, thenitrogen-containing aromatic cyclic compound penetrates between the πconjugated conductive polymer and the dopant to form a conductivecomposition.

The aforementioned conductive composition contains a π conjugatedconductive polymer, a dopant, and a nitrogen-containing aromatic cycliccompound. In this conductive compound, part of the nitrogen-containingaromatic cyclic compound partly coordinates or binds to protons orsubstituents from the dopant, being positively charged and becoming acation of the nitrogen-containing aromatic cyclic compound. Therefore, amixture of the nitrogen-containing aromatic cyclic compound cation andthe remaining nitrogen-containing aromatic cyclic compound is present inthe conductive composition. This mixture forms salts together withexcessive anion groups of the dopant, is attracted to the dopant,penetrate into the π conjugated conductive polymer of the conductivecomposition. The presence of the nitrogen-containing aromatic cycliccation compound and nitrogen-containing aromatic cyclic compound withinthe π conjugated conductive polymer causes the hopping energy for theelectric conductivity of the π conjugated conductive polymer to dropand, therefore, improve the electric conductivity.

The conductive composition also has excellent heat resistance andmoisture resistance.

The conductive cross-linked product of the present invention isdescribed below.

The conductive cross-linked product of the present invention is formedby heating and/or irradiating with ultraviolet ray a conductivecomposition containing a nitrogen-containing aromatic cyclic compoundhaving a cross-linkable functional group.

The conductive cross-linked product can be formed by, for example,applying a conductive composition solution to a base and removing thesolvent by an appropriate technique, which is followed by heating and/orUV irradiation.

The conductive composition solution can be applied by, for example,immersion, comma coating, spray coating, roll coating, or gravureprinting.

Either one or both of heat and UV irradiation treatments are selectedaccording to the type of the cross-linkable functional group. Heatingcan be done by a conventional technique such as hot air heating andinfrared heating. UV irradiation can done be by using a light sourcesuch as super high pressure mercury lamp, high pressure mercury lamp,low pressure mercury lamp, carbon arc, xenon arc, and metal halide lamp.

Because the cross-linkable nitrogen-containing aromatic cyclic compoundis cross-linked, the conductive cross-linked product is highly compact,consequently being not only highly conductive but also highly heatresistant, thermally stable, and solvent resistant.

An embodiment of the capacitor of the present invention and theproduction method thereof is described below.

FIG. 1 is an illustration to show the structure of a capacitor of thisembodiment. The capacitor 10 comprises an anode 11 composed of a porousbody of valve metal, a dielectric layer formed by oxidizing the surfaceof the anode 11, and a cathode provided on the dielectric layer.

<Anode>

The valve metal of anode 11 may be, for example, aluminum, tantalum,niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, orantimony. Among them, aluminum, tantalum, and niobium are preferred.

Specifically, the anode 11 may be an aluminum foil that is etched for anextended surface area and oxidized on the surface or a pellet formed bysintering tantalum or niobium particles and oxidizing the surface of thesintered mass. The anodes prepared in these ways have a rough surface.

<Dielectric Layer>

The dielectric layer 12 is formed by anodizing the surface of the anode11 in an electrolyte such as an aqueous ammonium adipate. As shown inFIG. 1, the dielectric layer 12 also has a rough surface like the anode11.

<Cathode>

The cathode 13 comprises a solid electrolyte layer 13 a and a cathodeconductive layer 13 b made of, for example, carbon, silver, or aluminumdeposited on the solid electrolyte layer 13 a. The solid electrolytelayer 13 a contains a π conjugated conductive polymer and provided onthe dielectric layer 12 side.

When the cathode conductive layer 13 b is made of carbon, silver, andthe like, it can be formed using a conductive paste containing carbon,silver, and the like. When the cathode conductive layer 13 b is made ofaluminum, it can be formed using, for example, aluminum foil.

A separator can be provided between the solid electrolyte layer 13 a andthe anode 11 where necessary.

The electron donor compound of a capacitor having an electron donorcompound layer containing an electron donor element is a compoundcontaining an electron donor element, not a polymer.

The electron donor element contained in an electron donor compound ispreferably at least one or more elements selected from nitrogen, oxygen,phosphorus, and sulfur among the elements in the groups 15 and 16 of theperiodic table of the elements because the electric affinity between thedielectric layer and the cathode containing a π conjugated conductivepolymer is improved.

The nitrogen-containing electron donor compound is preferably primaryamine, secondary amine, or tertiary amine for improved electric affinitybetween the dielectric layer and the cathode. Examples of aminesspecifically include aliphatic amines such as ethylamine, diethylamine,methylethylamine, and triethylamine, and aromatic amines such asaniline, benzylamine, pyrrole, imidazole, pyridine, pyrimidine,pyrazine, and triazine, and their derivatives.

The oxygen-containing electron donor compound may be, for example,alcohols, ethers, and ketones. Their examples specifically includelauryl alcohol, hexadecyl alcohol, benzyl alcohol, ethylene glycol,propylene glycol, glycerin, diphenyl ether, cyclohexane, diacetonealcohol, isophorone, furan, and their derivatives.

The phosphorus-containing electron donor compound may be, for example,phosphoric acid ester, phosphorous acid ester, phosphonic acid,alykylphosphine, or alykylphosphonium salt. Their examples specificallyinclude trimethyl phosphate, triphenyl phosphate, trimethyl phosphite,triethyl phosphite, dimethyl phosphonate, diethyl phosphonate,triethylphosphine, tri-n-butylphosphine, tri-n-butylphosphineoxide,tetraethylphosphoniumbromide, and tetra-n-butylphosphoniumbromide.

The sulfur-containing electron donor compound may be, for example,sulfides, thiols, isothiocyanates, thiophenes and their derivatives.Their examples specifically include dimethysulfide, diethylsulfide,methylmercaptan, ethylmercaptan, phenylisothiocyanate,n-butylisothiocyanate, thiophene, and 3-methylthiophene.

Among these electron donor compounds, compounds containing nitrogen,oxygen, or sulfur in the aromatic ring are preferred because theequivalent series resistance does not drop even though they remain inthe dielectric layer. Compounds containing nitrogen in the aromatic ringinclude pyrrole and their derivatives (pyrroles), imidazole, pyridine,pyrimidine, pyrazine, pyrazine, and triazine and their derivatives.Compounds containing oxygen in the aromatic ring include furan and theirderivatives (furans). Compounds containing sulfur in the aromatic ringinclude thiophene and their derivatives (thiophenes). Among these, atleast one compound selected from pyrroles, thiophenes, and furans ispreferable because the electric affinity between the dielectric layerand the cathode is improved.

The nitrogen, oxygen or sulfur atom of an electron donor compoundcontaining nitrogen, oxygen, or sulfur in the aromatic ring has anunshared electron pair. Therefore, a substituent or a proton is easilycoordinated or bound to these atoms. When a substituent or a proton iseasily coordinated or bound to the nitrogen, oxygen or sulfur atom, theatoms tend to be positively charged. The nitrogen, oxygen or sulfur atomis conjugated to another atom. The cationic charge generated by thesubstituent or proton coordinated or bound to these atoms is diffusedand stably present in the aromatic ring.

Therefore, electron donor compounds containing nitrogen, oxygen, orsulfur in the aromatic ring may be in the form of a cation with asubstituent being introduced in a nitrogen, oxygen, or sulfur atom.Further, the cation may form a salt together with an anion. Electrondonor compounds in the form of a salt exert the same effect asnon-cation electron donor compounds.

The aforementioned capacitor has an electron donor compound applied tothe dielectric layer surface. The dielectric layer surface isneutralized in terms of charge. Therefore, the electric affinity betweenthe dielectric layer and the solid electrolyte layer containing a πconjugated conductive polymer is improved. Consequently, the resistanceat the interface between the dielectric layer and the cathode isreduced; the capacitor has low impedance and high electrostaticcapacity.

(Production of a Capacitor)

An embodiment of the method of producing a capacitor of the presentinvention is described below.

An embodiment of the method of producing a capacitor, comprising thesteps of: a first step of oxidizing a surface of an anode composed of aporous material of valve metal and forming a dielectric layer; a secondstep of applying an electron donor compound containing an electron donorelement to a surface of the dielectric layer and forming an electrondonor compound layer; and a third step of forming a solid electrolytelayer containing a π conjugated conductive polymer on a surface of theelectron donor compound layer.

In the method of producing a capacitor, the anode surface can beoxidized by, for example, anodizing the anode surface in an electrolytesolution such as an aqueous ammonium adipate.

The electron donor compound can be applied to the dielectric layersurface by a known application technique such as coating, immersion, andspray. When the electron donor compound is in a solid form, the electrondonor compound is dissolved in a solvent before it is applied. In such acase, it is preferred that the solvent be removed through drying afterthe application. It is also preferred that the solvent be removed when aliquid electron donor compound is diluted for use.

The concentration of the electron donor compound is not limited.However, the effect may not be apparent when it is excessively low. Onthe other hand, the ESR may drop when it is excessively high. Theconcentration is preferably 1 to 80% by weight, more preferably 5 to 50%by weight.

A layer containing a π conjugated conductive polymer is preferablyformed by applying a conductive polymer solution of the π conjugatedconductive polymer dissolved in a solvent to the dielectric layersurface because it is simple and the electric affinity between thedielectric layer and cathode can be easily improved. Alternatively,precursor monomers composing a π conjugated conductive polymer can bedirectly chemical oxidative polymerized or electrolytic polymerized onthe dielectric layer.

A conductive polymer solution is obtained by polymerizing precursormonomers of a π conjugated conductive polymer in the presence ofanion-containing solubilizing polymer, or obtained by dissolving a πconjugated conductive polymer having solvent solubility into a solvent.

An example of a preparation method of a conductive polymer solution bypolymerizing precursor monomers of a π conjugated conductive polymer inthe presence of anion-containing solubilizing polymer, comprises thesteps of: dissolving an anion-containing solubilizing polymer into asolvent which is able to dissolve the polymer, adding precursor monomersof a π conjugated conductive polymer to the obtained solution,polymerizing the precursor monomers by adding an oxidant, and thenremoving the excess oxidant and precursor monomers and purifying toobtain the conductive polymer solution.

The usable anion-containing solubilizing polymers are selected from theabove-described examples.

The conductive polymer solution may contain a dopant except theanion-containing solubilizing polymer in order to improve conductivityof the π conjugated conductive polymer. The dopant is selected from theabove-described examples.

The ratio of a π conjugated conductive polymer and a dopant ispreferably 97:3 to 10:90 (π conjugated conductive polymer:dopant). Ifthe dopant content is over or under this range, conductivity of the πconjugated conductive polymer tends to decrease.

Examples of coating method of the conductive polymer solution includeknown methods such as coating, immersion, and spray, and dried by aknown technique such as hot air drying.

A capacitor is obtained by forming a cathode using known methods such asa method forming the solid electrolyte layer, penetrating theelectrolyte into the layer if necessary, and forming a cathodeconductive layer by applying carbon or silver paste, and a methodproviding the cathode conductive layer such as aluminum foil via aseparator.

When a separator is used, the separator can be a single or mixednon-woven fabric such as cellulose fiber, glass fiber, polypropylenefiber, polyester fiber, and polyamide fiber or carbide non-woven fabricsprepared by carbonizing them

In the aforementioned method of producing a capacitor, an electron donorcompound is applied to the dielectric layer surface, by which theelectric affinity between the dielectric layer and the solid electrolytelayer is improved and, therefore, the impedance can be reduced.Moreover, an electron donor compound is simply applied. Hence, accordingto the aforementioned method of producing a capacitor, a low impedancecapacitor can be produced in a simple manner.

Furthermore, capacitors produced by the aforementioned method have highelectrostatic capacity and excellent heat resistance.

The capacitor having an electron donor compound layer of the presentinvention is not limited to the aforementioned embodiment. In theaforementioned embodiment, an electron donor compound is applied to thedielectric layer surface, a solid electrolyte layer is formed, and,then, a conductive cathode layer is provided to form a cathode, by whicha capacitor is obtained. In the present invention, the cathodeconductive layer can be provided at any time. For example, an electrondonor compound is applied to the dielectric layer surface and a solidelectrolyte layer is formed after a conductive cathode layer is providedin a manner in which it faces the dielectric layer. In such a case, aseparator is preferably provided between the cathode conductive layerand the dielectric layer.

The electron donor compound can be applied to the dielectric layer sidesurface of the cathode conductive layer and the separator beside thedielectric layer surface.

Another embodiment of the method of producing a capacitor, comprising astep of applying a conductive polymer solution containing a π conjugatedconductive polymer, a dopant, a nitrogen-containing aromatic cycliccompound, and a solvent to a surface of a dielectric layer of acapacitor intermediate comprising an anode composed of a porous materialof valve metal and the dielectric layer formed by oxidizing a surface ofthe anode, and forming a coating.

A conductive polymer solution is prepared by dissolving an aniongroup-containing solubilizing polymer in a solvent that can dissolve thepolymer, adding precursor monomers for constituting the conductivepolymer such as un-substituted aniline or pyrrole or thiophene to theobtained solution, adding oxidant to polymerize the monomers, removingthe extra oxidant and monomers for refining, and adding anitrogen-containing aromatic cyclic compound to obtain a conductivepolymer solution.

Known oxidants can be used for polymerizing the conductive polymer,including metal halogen compounds such as iron (II) chloride, borontrifluoride, and aluminum chloride; peroxides such as hydrogen peroxideand benzoyl peroxide; persulfates such as potassium persulfate, sodiumpersulfate, and ammonium persulfate; ozone; and oxygen.

The conductive polymer solution can be applied by known methods such ascoating, immersion, and spray, and dried by known methods such as hotair drying.

After the solid electrolyte layer is formed, the layer may be penetratedwith the electrolyte, if necessary. Then, a cathode is formed by carbonor silver paste or a known technique such as providing a cathodeelectrode in the opposite position via a separator.

When a separator is used, the separator can be a single or mixednon-woven fabric such as cellulose fiber, glass fiber, polypropylenefiber, polyester fiber, and polyamide fiber or carbide non-woven fabricsprepared by carbonizing them.

In the aforementioned method, the conductive polymer solution is appliedand dried to form a solid electrolyte layer. Therefore, the process issimple and suitable for mass-production, and realizes low cost.Containing a π conjugated conductive polymer, a dopant, and anitrogen-containing aromatic cyclic compound, the conductive polymersolution provides a highly conductive solid electrolyte layer.

The solid electrolyte layer can be formed by chemical oxidativepolymerization or electrolytic polymerization where a simple and lowcost process is not emphasized.

In the chemical oxidative polymerization, a solution of precursormonomers for constituting a π conjugated conductive polymer, such assubstituted or un-substituted aniline or pyrrole or thiophene and anoxidant solution are prepared. A capacitor intermediate is alternatelyimmersed in these solutions to form the conductive polymer on thedielectric layer surface of the capacitor. The same oxidant can be used.

The dopant and nitrogen-containing aromatic cyclic compound can besimultaneously dissolved in the monomer solution or in the oxidantsolution. Alternatively, a solution of the dopant andnitrogen-containing aromatic cyclic compound in a solvent is allowed tosoak into the π conjugated conductive polymer after the π conjugatedconductive polymer is formed.

In the electrolytic polymerization, precursor monomers for constitutinga π conjugated conductive polymer such as un-substituted aniline,pyrrole, or thiophene are introduced in a solvent such as acetonitrile.A capacitor intermediate having a conductive layer formed on the surfaceis introduced in an electrolytic bath where dopant is added aselectrolyte. A higher voltage than the oxidation potential of theprecursor monomers is applied for polymerization, thereby a π conjugatedconductive polymer is formed on the dielectric layer of the capacitorintermediate.

The nitrogen-containing aromatic cyclic compound can be dissolved in theelectrolytic bath. Alternatively, a solution of the nitrogen-containingaromatic cyclic compound in a solvent can be allowed to soak into the πconjugated conductive polymer after the conductive polymer is formed.

When the solid electrolyte layer is formed by application of aconductive polymer solution or chemical oxidative polymerization, sincethe π conjugated conductive polymer has a large particle size, the πconjugated conductive polymer cannot reach deep inside the fine gaps onthe dielectric layer surface of the capacitor intermediate, making itdifficult to derive electrostatic capacity. It is preferred that thecathode has electrolyte and the electrolyte is allowed to soak into thedielectric layer so as to complement the electrostatic capacity.

When the nitrogen-containing aromatic cyclic compound has across-linkable functional group, it is preferred that the coating issubject to heating and/or UV irradiation after it is formed by applyinga conductive polymer solution. Either one or both of heating and UVirradiation are selected according to the type of the cross-linkablefunctional group.

Heating can be done by a conventional technique such as hot air heatingand infrared heating. UV irradiation can be done by using a light sourcesuch as super high pressure mercury lamp, high pressure mercury lamp,low pressure mercury lamp, carbon arc, xenon arc, and metal halide lamp.

[Electrolyte]

The electrolyte is not limited as long as it has a high electricconductivity. It can be a known electrolyte dissolved in a knownsolvent.

Examples of the solvent include water; alcohol solvents such as ethyleneglycol, diethylene glycol, propylene glycol, 1,4-butanediol, andglycerin; lactone solvents such as γ-butyrolactone, γ-valerolactone, andδ-valerolactone; amide solvents such as N-methylformamide,N,N-dimethylformamide, N-methylacetamide, and N-methylpyrrolidinone; andnitrile solvents such as acetonitrile, and 3-methoxypropionitrile.

Examples of the electrolyte include, as anion components, adipic acid,glutaric acid, succinic acid, benzoic acid, isophthalic acid, phthalicacid, terephthalic acid, maleic acid, toluic acid, enanthic acid,malonic acid, and formic acid; decandicarboxylic acid such as1,6-decanedicarboxylic acid and 5,6-decanedicarboxylic acid;octanedicarboxylic acids such as 1,7-octanedicarboxylic acid; organicacids such as azelaic acid and sebacic acid; or coral, coral polyalcoholcomplex compounds obtained from coral and polyalcohol; and inorganicacids such as phosphoric acid, carbonic acid, and silicic acid; and, ascation components, primary amine (methylamine, ethylamine, propylamine,butylamine, ethyleneamine); secondary amine (dimethylamine,diethylamine, dipropylamine, methylethylamine, diphenylamine); andtertiary amine (trimethylamine, triethylamine, tripropylamine,triphenylamine, 1,8-diazacyclo(5,4,0)-undecene-7), tetraalkylammonium(tetramethylammonium, tetraethylammonium, tetrapropylammonium,tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium).

Embodiments of the methods of producing an antistatic coating material,an antistatic coating, an antistatic film, an optical film, and anoptical information recording medium are described below.

[Production Method] (Antistatic Coating Material)

For producing an antistatic coating material, first, a solubilizingpolymer is dissolved in a solvent than can dissolve the polymer.Precursor monomers of a conductive compound and, where necessary, adopant are added and the mixture is well stirred.

An oxidant is added dropwise to the mixture to allow the polymerization,thereby a composite material of the conductive compound and thesolubilizing polymer is obtained. After removing the oxidant, monomerresidue, and byproducts and refining, the composite material isdissolved in an appropriate solvent. A nitrogen-containing aromaticcyclic compound and, where necessary, a dopant, a binder resin, and across-linkable compound are added to obtain an antistatic coatingmaterial.

A known oxidant can be used for polymerizing precursor monomers of aconductive polymer. Examples of the oxidant include metal halogencompounds such as iron (II) chloride, boron trifluoride, and aluminumchloride, peroxides such as hydrogen peroxide and benzoyl peroxide,persulfates such as potassium persulfate, sodium persulfate, andammonium persulfate, ozone, and oxygen.

Refining technique is not particularly limited. For example,reprecipitation and ultrafiltration can be used. Ultra-filtration ispreferred because it is simple. Ultra-filtration is a technique whereina solution is circulated on a porous ultrafiltration membrane, allowingthe liquid of the solution to permeate the membrane. In this technique,there is a difference in pressure between the circulating solution sideand the permeated solution side of the ultrafiltration membrane.Therefore, the circulating solution partly penetrates into the permeatedsolution side to alleviate the pressure on the circulating solutionside. Along with the penetration of the circulating solution, some ofthe particles having a particle size smaller than the ultrafiltrationmembrane opening and dissolved ions moves to the permeated solutionside, thereby the particles and dissolved ions are removed. Theultrafiltration membrane used can selectively have a differentialmolecular weight of 1000 to 1000000 according to the particle sizes andion types to be removed.

(Antistatic Coating)

An antistatic coating is formed by applying the antistatic coatingsolution to a base. The antistatic coating solution can be applied by,for example, immersion, comma coating, spray coating, roll coating, orgravure printing. The base is not limited. Molded resins, particularlyresin films, which are easily electro-statically charged, are preferred.

After application, the solution is heated to remove the solvent or heat-or photo-cured.

Heating can be done by a conventional technique such as hot air heatingand infrared heating. Photo-curing to form a coating can be done by UVirradiation using a light source such as super high pressure mercurylamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc,xenon arc, and metal halide lamp.

Containing a nitrogen-containing aromatic cyclic compound, theantistatic coating has a remarkably high conductivity. Specifically, theantistatic coating has an electric conductivity of approximately 10 to2000 S/cm when it contains a nitrogen-containing aromatic cycliccompound while the antistatic coating has an electric conductivity ofapproximately 0.001 to 100 S/cm when it does not contain anitrogen-containing aromatic cyclic compound. Therefore, higherconductivity is obtained even though it is itself a conductive polymer.

When the antistatic coating material contains a nitrogen-containingaromatic cyclic compound, the nitrogen-containing aromatic cycliccompound is cross-linked by heating or UV irradiation. The antistaticcoating is densely interconnected, consequently being not only highlyconductive but also more heat resistant and thermally stable.

When an antistatic coating is used in optical applications, particularlyin optical filters and optical information recording media describedlater, it is preferred that the antistatic coating be highlytransparent. Specifically, the antistatic coating preferably has a totallight transmittance (JIS Z 8701) of 85% or higher, more preferably 90%or higher, most preferably 96% or higher. The antistatic coatingpreferably has a haze (JIS K 6714) of 5% or lower, preferably 3% orlower, most preferably 1% or lower.

When the antistatic coating also serves as a hard coat layer, theantistatic coating preferably has a surface hardness (pensile hardness)of HB or harder.

The surface resistance of the antistatic coating is preferably adjustedas appropriate in view of optical properties. Generally, approximately1×103Ω to 1×1012Ω is preferable for antistatic use.

The total light transmittance, haze, and surface resistance of a coatingcan be adjusted by the thickness of the antistatic coating. It ispreferred to exclude binder resins where a lower surface resistance isrequired. However, it is preferred to contain binder resins where lowcost and better adhesion to a base are required.

(Antistatic Film)

An antistatic film comprises a base film and the aforementionedantistatic coating on at least one side of the base film.

[Substrate Film]

Examples of the base film include low density polyethylene film, highdensity polyethylene film, ethylene-propylene copolymer film,polypropylene film, ethylene-vinyl acetate copolymer film,ethylene-methylmethacrylate copolymer film, polyethyleneterephthalate(PET) film, polybutyleneterephthalate (PBT) film,polyethylenenaphthalate (PEN) film, polyimide film, 6-nylon film,6,6-nylon film, polymethylmethacrylate film, polystyrene film,styrene-acrylonitrile-butadiene copolymer film, polyacrylonitrile film,cellulose triacetate (TAC) film, cellulose propionate film, polyvinylchloride film, polyvinylidene chloride film, polyvinylidene fluoridefilm, polyethylene tetrafluoride film, polyvinyl alcohol coating film,ethylene-vinyl alcohol copolymer film, polycarbonate film, polysulfonefilm, polyethersulfone film, polyetherether ketone film, andpolyphenyleneoxide film.

These base films generally have lipophilic surfaces. Therefore, it isdifficult to apply an antistatic coating dissolved in an aqueoussolvent. Then, when an antistatic coating material dissolved in anaqueous solvent is used, it is preferred that the base film surface betreated by, for example, etching such as sputtering, corona discharge,blazing, UV irradiation, electron irradiation, chemical conversion, andoxidation or base coating for hydrophilicity. Furthermore, solventcleaning or ultrasonic cleaning may be performed for ducting and cleanupwhere necessary.

(Optical Filter)

An embodiment of the optical filter of the present invention isdescribed below.

FIG. 2 shows an optical filter of this embodiment. An optical filter 20comprises a film base 21, an antistatic coating 22 formed on the filmbase 21, and an anti-reflection layer 23 formed on the antistatic layer22. The antistatic coating 22 of the optical filter 20 also serves as ahard coat layer.

In order to attach the optical filter 20 to the display screen of adisplay apparatus, a transparent adhesive layer is provided on thesurface of the film base 21 of the optical filter 20 and the opticalfilter is attached via this adhesive layer.

Any type of transparent plastic films can be used as the film base 21.Examples of transparent plastic films include those made of polyethyleneterephthalate, polyimide, polyethersulfone, polyetheretherketone,polycarbonate, polypropylene, polyamide, acrylamide, cellulose, andpropionate.

It is preferred that the film base has a surface treated by, forexample, etching such as sputtering, corona discharge, blazing, UVirradiation, electron irradiation, chemical conversion, and oxidation orprimary coating. With the surface being thus treated, the film base hasbetter adhesion to the antistatic coating 22.

The surface of the film base 21 can be cleaned by solvent cleaning orultrasonic cleaning for ducting and cleanup where necessary before theantistatic coating 22 is attached.

The antistatic coating 22 is a coating made of an antistatic coatingmaterial as described above and also serves as a hard coat layer.Therefore, as mentioned above, it is preferred that the antistaticcoating 22 has a surface hardness (pencil hardness) of HB or harder.Further, because of optical use, the antistatic coating 22 preferablyhas a total light transmittance (JIS Z 8701) of 85% or higher, morepreferably 90% or higher, most preferably 96% or higher. The antistaticcoating 20 preferably has a haze (JIS K 6714) of 5% or lower, preferably3% or lower, and most preferably 1% or lower.

The anti-reflection layer 23 prevents light reflection. This layer canbe a monolayer or a multilayer. When it is a monolayer, it is preferredthat the anti-reflection layer has a refractive index of 1.38 to 1.45and an optical film thickness of 80 to 100 nm.

The anti-reflection layer 23 can be formed by a dry or wet method.Examples of the dry method include physical vapor deposition such aselectron beam deposition, dielectric heating deposition, resistanceheating deposition, sputtering, and ion plating and plasma CVD. When itis formed by a dry method, the anti-reflection layer 23 can containinorganic compound components such as silicon oxide, magnesium oxide,niobium oxide, titanium oxide, tantalum oxide, aluminum oxide, zirconiumoxide, indium oxide, and tin oxide.

In the wet method, a coating material containing a curable compound isapplied by a known technique such as comma coating, spray coating, rollcoating, and gravure printing and, then, cured. Usable curable compoundsfor forming the anti-reflection layer 23 by a wet method includefluorine-containing compounds such as fluorine-containing organiccompounds, fluorine-containing organic silicon compounds, andfluorine-containing inorganic compounds.

The optical filter 20 can further comprise an anti-fouling layer on theanti-reflection layer 23. The anti-fouling layer serves to prevent dustand stain and make cleaning easy when it gets dirt.

The anti-fouling layer is not particularly limited as long as it doesnot interfere with the anti-reflection function of the anti-reflectionlayer 23 and is highly water repellent and oil repellent. It can be anorganic compound layer or an inorganic compound layer. The anti-foulinglayer can be, for example, a layer containing an organic siliconcompound having a perfluorosilane or fluorocycloalkyl group or afluorine organic compound.

The anti-fouling layer can be formed by a techniques selected accordingto its type, including physical vapor phase deposition method orchemical vapor phase deposition method such as vapor deposition,sputtering, and ion plating, vacuum process such as plasmapolymerization, micro gravure, screen coating, and dip coating.

The aforementioned optical filter 20 has the antistatic coating 22 forprotecting the film base 21. The antistatic coating 22 is made of theaforementioned antistatic coating material, being highly transparent andshowing good adhesion to the film base 21. The optical filter 20 has astable antistatic property, which keeps dust away from it.

The optical filter 20 as described above can be preferably used inanti-reflection films for liquid crystal displays and plasma displays,infrared absorptive films, and electromagnetic wave absorptive films.

The optical filter of the present invention is not limited to theaforementioned embodiment as long as it has an antistatic coating madeof the aforementioned antistatic coating material. For example, the filmbase can be replaced with a polarizing plate. The polarizing plate canbe a laminate of a polyvinyl alcohol resin film in which a dichromaticcolorant is absorbed and oriented and a protective film(s) on one orboth sides of the film. Iodine or a dichromatic dye can be used as thedichromatic colorant. Such a filter can be provided to the most frontsurface of a liquid crystal display.

(Optical Information Recording Medium)

An embodiment of the optical information recording medium of the presentinvention is described below.

FIG. 3 shows an optical information recording medium of this embodiment.An optical information recording medium 30 is a rewritable diskcomprising a transparent resin disc base 31 made of polycarbonate orpolymethylmethacrylate, a first dielectric layer 32, an opticalinformation recording layer 33, a second dielectric layer 34, a metalreflection layer 35, and an antistatic layer 36, which are formed insequence.

The first and second dielectric layers 32 and 34 can be made ofinorganic materials such as SiN. SiO, SiO2, and Ta2O5.

These dielectric layers can be formed to a thickness of 10 to 500 nm bya known technique such as vacuum deposition, sputtering, and ionplating.

The optical information recording layer 33 can be made of, for example,inorganic photomagnetic recording materials such as Tb—Fe, Tb—Fe—Co,Dy—Fe—Co, and Tb—Dy—Fe—Co, inorganic phase-conversion recordingmaterials such as TeOx, Te—Ge, Sn—Te—Ge, Bi—Te—Ge, Sb—Te—Ge, Pb—Sn—Te,and Tl—In—Se, and organic dyes such as cyanine dye, polymethine dye,phthalocyanine dye, merocyanine dye, azulene dye, and squalium dye.

When it is made of an inorganic material, the optical informationrecording medium 33 can be formed to a thickness of 10 to 999 nm by aknown technique such as vacuum deposition, sputtering, and ion plating.When it is made of an organic dye, the optical information recordingmedium 33 can be formed by applying a solution of the organic dye in asolvent such as acetone, diacetone alcohol, ethanol, and methanol usinga known printing or application technique to a thickness of 10 to 999nm.

The metal reflection layer 35 reflects light. It is made of metals suchas Al, Cr, Ni, Ag, and Au and their oxides and nitrides. They can beused individually or in combination of two or more. The metal reflectionlayer 35 is formed by sputtering or vacuum deposition to a thickness of2 to 200 nm.

The antistatic coating 36 is made of the aforementioned antistaticcoating material. Having a surface hardness of HB or harder, theantistatic coating 36 serves to protect the surface of the opticalinformation recording medium 30 from being damaged, to protect the metalreflection layer 35 from being oxidized, and to prevent adhesion of dustcaused by static electricity.

The antistatic coating 36 preferably has a thickness of 3 to 15 μm. Whenthe thickness is smaller than 3 μm, it is often difficult to form auniform coating; thereby the antistatic coating may fail to providesufficient antistatic or damage resistant property or antioxidationeffect on the metal reflection layer 35. When the thickness is largerthan 15 μm, the inner stress is increased. Therefore, the opticalinformation recording medium 30 may have deteriorated mechanicalproperties.

The antistatic coating 36 can be formed by applying the antistaticcoating material to the metal reflection layer 35 using a knowntechnique such as comma coating, spray coating, roll coating, andgravure printing, which is followed by drying the solvent or heat- orUV-curing.

The aforementioned optical information recording medium 30 has theantistatic coating 36 that serves to protect the optical informationrecording layer 33 and metal reflection layer 35. The antistatic coating36 is made of the aforementioned antistatic coating material. Therefore,the antistatic coating 36 has a small haze and a high lighttransmittance, being highly transparent at reading laser wavelengths of780 and 635 nm. With its antistatic property, the antistatic coating 36serves to control dust adhesion caused by static electricity and,therefore, prevent reading and writing errors.

The optical information recording medium of the present invention is notlimited to the aforementioned embodiment. For example, it can be arecordable disc. The recordable disc comprises, for example, atransparent resin base (organic material), an optical informationrecording layer, a reflection metal layer, and an antistatic coating,which are formed in sequence.

EXAMPLES

Examples of the present invention are described below. However, thepresent invention is not limited to these examples.

Conductive Composition Preparation Example 1 Preparation ofPolyisoprenesulfonic Acid

Sodium isoprenesulfonate in the amount of 171 g (1 mol) was dissolved in1000 ml of ion-exchanged water. An oxidant solution of 1.14 g (0.005mol) of ammonium persulfate previously dissolved in 10 ml of water wasadded in drops to the solution over 20 minutes while stirring at 80° C.The solution was stirred for 12 hours.

10% by weight diluted sulfuric acid in the amount of 1000 ml was addedto the obtained sodium isoprenesulfonate polymer solution andapproximately 1000 ml of sodium isoprenesulfonate solution was removedby ultrafiltration. An amount of 2000 ml of ion-exchanged water wasadded to the remaining solution and approximately 2000 ml of thesolution was removed by ultrafiltration. This ultrafiltration operationwas repeated three times.

Then, approximately 2000 ml of ion-exchanged water was added to theobtained filtrate and approximately 2000 ml of the solution was removedby ultrafiltration. This ultrafiltration operation was repeated threetimes.

The ultrafiltration conditions were as follows (the same was applied tothe other examples).

Differential molecular weight of the ultrafiltration membrane: 30K

Cross Flow System

Feed rate: 3000 ml/min.

Membrane partial pressure: 0.12 Pa

Water in the obtained solution was removed under reduced pressure toobtain a colorless solid material.

Preparation Example 2 Preparation of Polystyrenesulfonic Acid

Sodium styrenesulfonate in the amount of 206 g (1 mol) was dissolved in1000 ml of ion-exchanged water. An oxidant solution of 1.14 g (0.005mol) of ammonium persulfate previously dissolved in 10 ml of water wasadded in drops to the solution over 20 min. while stirring at 80° C. Thesolution was stirred for 12 hours.

10% by weight diluted sulfuric acid in the amount of 1000 ml and waterin the amount of 15000 ml were added to the obtained sodiumstyrenesulfonate solution and approximately 13000 ml of sodiumstyrenesulfonate solution was removed by ultrafiltration. 12000 ml ofion-exchanged water is added to the remaining solution and approximately13000 ml of the solution was removed by ultrafiltration. Thisultrafiltration operation was repeated three times.

Then, approximately 12000 ml of ion-exchanged water was added to theobtained filtrate and approximately 13000 ml of the solution was removedby ultrafiltration. The ultrafiltration operation was repeated threetimes.

Example 1

The amount of 14.2 g (0.1 mol) of 3,4-ethylenedioxythiophene and asolution of 27.5 g (0.15 mol) of polystyrenesulfonic acid in 2000 ml ofion-exchanged water were mixed at 20° C.

An oxidation catalysis solution of 29.64 g (0.13 mol) of ammoniumpersulfate and 8.0 g (0.02 mol) of iron (II) sulfate in 200 ml ofion-exchanged water was slowly added to the mixed solution whilemaintaining at 20° C. and stirring. Then, the mixture was stirred andallowed to react for 3 hours.

Ion-exchanged water in the amount of 2000 ml was added to the obtainedreaction solution and approximately 2000 ml of the solution was removedby ultrafiltration. This operation was repeated three times.

Diluted sulfuric acid in the amount of 200 ml of 10% by weight and 2000ml of ion-exchanged water were added to the ultra-filtered solution andapproximately 2000 ml of the solution was removed by ultrafiltration.The amount of 2000 ml of ion-exchanged water was added and approximately2000 ml of the solution was removed. This operation was repeated threetimes.

Then, 2000 ml of ion-exchanged water was added to the obtained solutionand approximately 2000 ml of the solution was removed byultrafiltration. This operation was repeated five times. Approximately1.5% by weight of blue polystyrenesulfonic acid dopedpoly(3,4-ethylenedioxythiophene) was obtained. This was indicated as a πconjugated conductive polymer solution A.

The amount of 0.56 g of imidazole was uniformly dispersed in 100 ml ofthe obtained π conjugated conductive polymer solution A to obtain aconductive composition solution.

The components used are shown in Table 1.

The conductive composition solution was applied to a glass and dried inan oven at 150° C. to obtain a coating of the conductive composition.The obtained coating was evaluated for electric properties by thefollowing evaluation method. The results are shown in Table 2.

TABLE 1 π conjugated conductive Nitrogen-containing polymer Dopantaromatic cyclic compound Example 1 poly(3,4-ethylenedioxy-polystyrenesulfonic imidazole Example 2 thiophene) acid Example 3Example 4 Example 5 1,2-dimethylimidazole Example 6 Example 7 Example 8pyridinesulfonic acid Example 9 polyisoprenesulfonic imidazole acidExample 10 polypyrrole polystyrenesulfonic imidazole acid Example 11polyisoprenesulfonic acid Comparative polypyrrole polyacrylic acid —Example 1 Comparative poly(3,4-ethylenedioxy- polystyrenesulfonic —Example 2 thiophene) acid Comparative polyisoprenesulfonic — Example 3acid Comparative polypyrrole polystyrenesulfonic — Example 4 acid

(Evaluation Method)

Electric conductivity (S/cm):

The electric conductivity of the coatings was measured by LORESTA(manufactured by Mitsubishi Chemical Corporation).

Retention rate of electrical conductivity depending on heat (%):

The electric conductivity R25B of the coatings was measured by LORESTA(manufactured by Mitsubishi Chemical Corporation) at a temperature of25° C. Then, the coating was allowed to stand at 125° C. for 300 hours.The temperature of the coating was returned to 25° C. and the electricconductivity R25A was measured. The obtained values were applied to thefollowing equation to obtain a retention rate of electric conductivitydepending on heat. The retention rate of electric conductivity dependingon heat is an indicator for heat resistance.

Retention rate of electric conductivity depending on heat(%)=100×R25A/R25B

Rate of change of electric conductivity depending on humidity (%):

The electric conductivity R25B of the coatings was measured at 25° C.and at a humidity of 60% RH. Then, the coating was allowed to stand at180° C. and 90% RH for 200 hours. The temperature of the coating wasreturned to 25° C. and 60% RH and the electric conductivity R25A wasmeasured. The obtained values were applied to the following equation toobtain a rate of change of electric conductivity depending on humidity.The rate of change of electric conductivity depending on humidity is anindicator for moisture resistance.

Rate of change of electric conductivity depending on humidity(%)=100×(R25B−R25A)/R25B

TABLE 2 Retention rate Rate of change of electric of electric Electricconductivity conductivity conductivity depending on depending on (S/cm)heat (%) humidity (%) Example 1 150 23.5 5.5 Example 2 316 47 4.3Example 3 412 44.2 4.1 Example 4 373 49.1 5.2 Example 5 242 85.4 3.0Example 6 198 83 2.7 Example 7 186 87.2 4.2 Example 8 112 97.3 10.5Example 9 257 34.3 3.2 Example 10 163 38.5 3.5 Example 11 172 32.1 2.9Comparative 0.25 0.8 −380 Example 1 Comparative 5.6 12.5 −480 Example 2Comparative 2.3 8.7 −491 Example 3 Comparative 5.1 0.7 −416 Example 4

Examples 2 to 4

Using the π conjugated conductive polymer A obtained in Example 1,conductive composition coatings were obtained and evaluated in the samemanner as in Example 1 except that 1.67 g (Example 2), 2.79 g (Example3), or 5.57 g (Example 4) of imidazole was added in place of 0.56 g. Theresults are shown in Table 2.

Examples 5 to 7

Conductive composition coatings were obtained and evaluated in the samemanner as in Example 1 except that 2.36 g (Example 5), 3.93 g (Example6), or 7.67 g (Example 7) of 1,2-dimethylimidazole was added to 100 mlof the π conjugated conductive polymer A obtained in Example 1 in placeof imidazole. The results are shown in Table 2.

Example 8

A conductive composition coating was obtained and evaluated in the samemanner as in Example 1 except that 1.3 g of pyridinesulfonic acid wasadded to 100 ml of the π conjugated conductive polymer A obtained inExample 1 in place of imidazole. The results are shown in Table 2.

Example 9

A solution of polyisoprenesulfonic acid dopedpoly(3,4-ethylenedioxythiophene) was obtained in the same manner as inExample 1 except that 22.2 g (0.15 mol) of polyisoprenesulfonic acid wasused in place of polystyrenesulfonic acid. The solution was diluted to1.5% by weight with ion-exchanged water to obtain a π conjugatedconductive polymer solution B.

The amount of 1.67 g of imidazole was uniformly dispersed in 100 ml ofthe π conjugated conductive polymer solution B to obtain a conductivecomposition solution. The conductive composition solution was applied toa glass and dried in an oven at 150° C. to obtain a conductivecomposition coating. The obtained coating was evaluated for electricproperties in the same manner as in Example 1. The results are shown inTable 2.

Example 10

The amount of 6.8 g (0.1 mol) of pyrrole and a solution of 27.5 g (0.15mol) of polystyrenesulfonic acid in 2000 ml of ion-exchanged water weremixed and cooled to 0° C.

An oxidation catalysis solution of 29.64 g (0.13 mol) of ammoniumpersulfate and 8.0 g (0.02 mol) of iron (II) sulfate in 200 ml ofion-exchanged water was slowly added to the mixed solution whilemaintaining at 20° C. and stirring. Then, the mixture was stirred andallowed to react for 3 hours.

The obtained reaction solution was treated in the same manner as inExample 1 to obtain a polystyrenesulfonic acid doped polypyrrolesolution. The solution was diluted to 1.5% by weight with ion-exchangedwater to obtain a π conjugated conductive polymer solution C.

The amount of 1.67 g of imidazole was uniformly dispersed in 100 ml ofthe π conjugated conductive polymer solution C to obtain a conductivecomposition solution. The conductive composition solution was applied toa glass and dried in an oven at 150° C. to obtain a conductivecomposition coating. The obtained coating was evaluated for electricproperties in the same manner as in Example 1. The results are shown inTable 2.

Example 11

A polyisoprenesulfonic acid doped polypyrrole solution was obtained inthe same manner as in Example 1 except that 22.2 g (0.15 mol) ofpolyisoprenesulfonic acid was used in place of polystyrenesulfonic acid.The solution was diluted to 1.5% by weight with ion-exchanged water toobtain a π conjugated conductive polymer solution D.

The amount of 1.67 g of imidazole was uniformly dispersed in 100 ml ofthe π conjugated conductive polymer solution D to obtain a conductivecomposition solution. The conductive composition solution was applied toa glass and dried in an oven at 150° C. to obtain a conductivecomposition coating. The obtained coating was evaluated for electricproperties in the same manner as in Example 1. The results are shown inTable 2.

Comparative Example 1

The amount of 6.8 g (0.1 mol) of pyrrole and a solution of 10.8 g (0.15mol) of polyacrylic acid in 1000 ml of ion-exchanged water were mixedand cooled to 0° C.

An oxidation catalysis solution of 29.64 g (0.13 mol) of ammoniumpersulfate and 8.0 g (0.02 mol) of iron (II) sulfate in 200 ml ofion-exchanged water was slowly added to the mixed solution whilemaintaining at 20° C. and stirring. Then, the mixture was stirred andallowed to react for 3 hours.

The obtained reaction solution was adjusted to pH 10 with aqueousammonia (25% by weight), allowed to precipitate with isopropyl alcohol,and filtered. The filtrate was rinsed with ion-exchanged water threetimes. The filtrate was again dispersed in 1000 ml of ion-exchangedwater to obtain an aqueous polyacrylic acid-polypyrrole colloidsolution. The aqueous polyacrylic acid-polypyrrole colloid solution wasapplied to a glass and dried in an oven at 150° C. to obtain aconductive composition coating. The obtained coating was evaluated inthe same manner as in Example 1. The results are shown in Table 2.

Comparative Examples 2 to 4

The π conjugated conductive polymer solution A obtained in Example 1(polystyrenesulfonic acid doped poly(3,4-ethylenedioxythiophene)(PSS-PEDOT)), the π conjugated conductive polymer solution B obtained inExample 9 (polyisoprenesulfonic acid dopedpoly(3,4-ethylenedioxythiophene) (PIPS-PEDOT)), and the π conjugatedconductive polymer solution C obtained in Example 10(polystyrenesulfonic acid doped polypyrrole (PSS-PPY)) were applied toglasses as they were and dried in an oven at 150° C. to obtainconductive composition coatings. The obtained coatings were evaluatedfor electric properties in the same manner as in Example 1. The resultsare shown in Table 2.

Example 12

The amount of 3.16 g of N-vinylimidazole was added to 100 ml of the πconjugated conductive polymer solution A obtained in Example 1 in placeof imidazole to obtain a π conjugated conductive polymer solution D.Using the π conjugated conductive polymer solution D, a conductivecomposition coating was obtained and evaluated in the same manner as inExample 1. The results are shown in Table 4.

Table 3 shows π conjugated conductive polymers, nitrogen-containingaromatic cyclic compounds, and cross-linkable compounds used in Examples12 to 24.

TABLE 3 π conjugated Nitrogen-containing conductive polymer aromaticcyclic compound Cross-linkable compound Example 12poly(3,4-ethylenedioxy- N-vinylimidazole — Example 13 thiophene)2-hydroxyethylacrylate (UV polymerization) Example 142-hydroxyethylacrylate (thermal polymerization) Example 151-allylimidazole — Example 16 1-(2-hydoxyethyl)- — imidazole Example 17imidazole-4- — carboxylic acid Example 18 1-(2-hydroxyethyl)-5-sulfoisophthalic acid imidazole Example 19 1-(2-hydroxyethyl)-5-sulfoisophthalic acid imidazole Example 20 imidazole-4- ethyleneglycol carboxylic acid Example 21 1-(2-hydroxyethyl)- ethylene glycolimidazole Example 22 2-vinylpyridine — Example 23 polypyrroleN-vinylimidazole — Example 24 2-hydroxyethylacrylate

Example 13

A conductive composition solution was obtained in the same manner as inExample 1 except that 3.16 g of N-vinylimidazole was added to 100 ml ofthe π conjugated conductive polymer solution A obtained in Example 1 inplace of imidazole and 3.0 g of 2-hydroxyethylacrylate and 0.01 g of1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-1-propane-1-on (UVpolymerization initiator) were further added. The obtained solution wasapplied to a glass, dried in an oven at 100° C. to remove moisture, andUV irradiated by a UV irradiator to obtain a conductive compositioncoating. The obtained coating was evaluated. The results are shown inTable 4.

Example 14

A conductive composition coating was obtained and evaluated in the samemanner as in Example 1 except that 3.16 g of N-vinylimidazole was addedto 100 ml of the π conjugated conductive polymer solution A obtained inExample 1 in place of imidazole and 3.0 g of 2-hydroxyethylacrylate and0.02 g of ammonium persulfate (thermal polymerization initiator) werefurther added. The results are shown in Table 4.

Example 15

A conductive composition coating was obtained and evaluated in the samemanner as in Example 1 except that 3.83 g of 1-allylimidazole was addedto 100 ml of the π conjugated conductive polymer solution A obtained inExample 1 in place of imidazole. The results are shown in Table 4.

Example 16

A conductive composition coating was obtained and evaluated in the samemanner as in Example 1 except that 3.97 g of1-(2-hydroxyethyl)-imidazole was added to 100 ml of the π conjugatedconductive polymer solution A obtained in Example 1 in place ofimidazole. The results are shown in Table 4.

Example 17

A conductive composition coating was obtained and evaluated in the samemanner as in Example 1 except that 3.97 g of imidazole-4-carboxylic acidwas added to 100 ml of the π conjugated conductive polymer solution Aobtained in Example 1 in place of imidazole. The results are shown inTable 4.

Example 18

A conductive composition coating was obtained and evaluated in the samemanner as in Example 16 except that 1.2 g of 5-sulfoisophthalic acid wasfurther added to 50 ml of the π conjugated conductive polymer solution Aobtained in Example 16. The results are shown in Table 4.

Example 19

A conductive composition coating was obtained and evaluated in the samemanner as in Example 16 except that 1.2 g of 5-sulfoisophthalic acid and2.0 g of polyester solution (brand name: PLASCOAT Z-561, manufactured byGoo Chemical Co., Ltd.) were added to 50 ml of the π conjugatedconductive polymer solution A obtained in Example 16. The results areshown in Table 4.

Example 20

A conductive composition coating was obtained and evaluated in the samemanner as in Example 17 except that 0.25 g of ethylene glycol wasfurther added to 50 ml of the π conjugated conductive polymer solution Aobtained in Example 17. The results are shown in Table 4.

Example 21

A conductive composition coating was obtained and evaluated in the samemanner as in Example 16 except that 0.25 g of ethylene glycol and 1.8 gof polyurethane solution (brand name: REZAMINE D-4080, manufactured byDainichiseika Color & Chemicals Mfg. Co., Ltd.) were further added to 50ml of the π conjugated conductive polymer solution A obtained in Example16. The results are shown in Table 4.

Example 22

A conductive composition coating was obtained and evaluated in the samemanner as in Example 1 except that 1.8 g of 2-vinylpyridine was added to100 ml of the π conjugated conductive polymer solution A obtained inExample 1 in place of N-vinylimidazole. The results are shown in Table4.

Example 23

A conductive composition coating was obtained and evaluated in the samemanner as in Example 10 except that 4.73 g of N-vinylimidazole wasuniformly dispersed in 100 ml of the π conjugated conductive polymersolution C obtained in Example 10 in place of 1.67 g of imidazole. Theresults are shown in Table 4.

Example 24

A conductive composition coating was obtained and evaluated in the samemanner as in Example 10 except that 4.73 g of N-vinylimidazole wasuniformly dispersed in 100 ml of the π conjugated conductive polymersolution C obtained in Example 10 in place of 1.67 g of imidazole and2-hydroxyethylacrylate was further added. The results are shown in Table4.

TABLE 4 Retention rate Rate of change of electric of electric Electricconductivity conductivity conductivity depending on depending on (S/cm)heat (%) humidity (%) Example 12 382 54.3 10.3 Example 13 272 63.8 4.5Example 14 365 61.0 2.5 Example 15 294 57.2 8.9 Example 16 231 49.0 9.3Example 17 175 47.0 15.0 Example 18 235 35.0 3.2 Example 19 134 89.0 3.7Example 20 325 79.4 −1.0 Example 21 274 61.3 5.5 Example 22 179 49.3 9.3Example 23 89 42.0 8.7 Example 24 143 47.5 5.4

Every conductive compositions of Examples 1 to 24, which contained a πconjugated conductive polymer, a dopant, and a nitrogen-containingaromatic cyclic compound, had high electric conductivities. They alsohad high retention rate of electric conductivity depending on heat andwere stable for temperature changes. Electric conductivity was notincreased at high temperatures and high humidity, which indicated thatthe compositions also had excellent moisture resistance. Particularly,the conductive compositions of Examples 12 to 14, which contained anitrogen-containing aromatic cyclic compound having a cross-linkablefunctional group, were highly heat-stable. Further, their stability canbe further improved by additional use of other cross-linkable compounds.

On the other hand, the conductive compositions of Comparative Examples 1to 4, which did not contain nitrogen-containing aromatic cycliccompounds, had electric conductivities two orders lower than Examples.The retention rate of electric conductivity depending on heat wasextremely low and the rate of change of electric conductivity dependingon humidity was high.

[Capacitor]

Preparation Example 3 Preparation of a Conductive Polymer Solution

The amount of 14.2 g (0.1 mol) of 3,4-ethylenedioxythiophene and asolution of 27.5 g (0.15 mol) of polystyrenesulfonic acid (molecularweight: approximately 150000) in 2000 ml of ion-exchanged water weremixed at 20° C.

An oxidation catalysis solution of 29.64 g (0.13 mol) of ammoniumpersulfate and 8.0 g (0.02 mol) of iron (II) sulfate in 200 ml ofion-exchanged water was slowly added to the mixed solution whilemaintaining at 20° C. and stirring. Then, the mixture was stirred andallowed to react for 3 hours.

The obtained reaction solution was dialyzed to remove unreacted monomersand oxidant. A conductive polymer solution containing approximately 1.5%by weight of blue polystyrenesulfonic acid dopedpoly(3,4-ethylenedioxythiophene) was obtained.

Preparation Example 4 Preparation of an Electron Donor Compound Solution

The amount of 7.79 g of imidazole was dissolved in 100 ml of distilledwater to obtain an electron donor compound solution.

Preparation Example 5 Preparation of an Electron Donor Compound Solution

The amount of 10 g of pyrrole was dissolved in 100 ml ofmethylethylketone to obtain an electron donor compound solution.

Example 25

An etched aluminum foil was connected to an anode lead terminal andsubject to chemical conversion (oxidation) in 10% by weight of ammoniumadipate in water to form a dielectric layer on the aluminum foilsurface, by which an anode foil was obtained.

A cellulose separator was inserted between the anode foil and a facingaluminum cathode foil welded to a cathode lead terminal, which was thenrolled up to obtain a capacitor element.

The capacitor element was immersed in the electron donor compoundsolution prepared in Preparation Example 4 under reduced pressure anddried in a hot air drier at 120° C. for two minutes. Then, the capacitorelement was immersed in the conductive polymer solution prepared inPreparation Example 3 under reduced pressure and dried in a hot airdrier at 150° C. for 10 minutes. The immersion in the conductive polymersolution was repeated five times to form a solid electrolyte layercontaining a π conjugated conductive polymer on the dielectric layersurface.

Then, the capacitor element having the solid electrolyte layer wasmounted in an aluminum case and sealed with a sealing rubber to obtain acapacitor.

The electrostatic capacity at 120 Hz, initial equivalent seriesresistance (ESR) at 100 kHz, ESR at 125° C. and after 1000 hours of theobtained capacitor were measured. The results are shown in Table 5. TheESR is an indicator for impedance.

TABLE 5 Comparative Example 25 Example 26 Example 5 Electrostaticcapacity (μm) 47.8 46.2 3.4 ESR (mΩ) Initial 15 22 587 125° C., after 2131 1035 1000 hours

Example 26

A capacitor was obtained in the same manner as in Example 25 except thatthe electron donor compound solution prepared in Preparation Example 5was used. The capacitor was evaluated in the same manner as in Example25. The results are shown in Table 5.

Comparative Example 5

A capacitor was obtained and evaluated in the same manner as in Example25 except that the capacitor element was not immersed in the electrondonor compound solution. The results are shown in Table 5.

The capacitor of Examples 25 and 26 wherein the electron donor compoundwas applied to the dielectric layer surface had high electrostaticcapacities and low ESRs (low impedances). In addition, the ESRs afterheated were prevented from decreasing; the capacitor had excellent heatresistance.

On the other hand, the capacitor of Comparative Example 1 wherein theelectron donor compound was not applied to the dielectric layer surfacehad a low electrostatic capacity and high ESRs (high impedances). Inaddition, the ESRs after heated were significantly increased afterheated; the capacitor had low heat resistance.

Preparation Example 6 Preparation of a Conductive Polymer Solution

The amount of 14.2 g (0.1 mol) of 3,4-ethylenedioxythiophene and asolution of 27.5 g (0.15 mol) of polystyrenesulfonic acid (molecularweight: approximately 150,000) in 2000 ml of ion-exchanged water weremixed at 20° C.

An oxidation catalysis solution of 29.64 g (0.13 mol) of ammoniumpersulfate and 8.0 g (0.02 mol) of iron (II) sulfate in 200 ml ofion-exchanged water was slowly added to the mixed solution whilemaintaining at 20° C. and stirring. Then, the mixture was stirred andallowed to react for 3 hours.

The obtained reaction solution was dialyzed to remove unreacted monomersand oxidant. A solution containing approximately 1.5% by weight of bluepolystyrenesulfonic acid doped poly(3,4-ethylenedioxythiophene) wasobtained. Then, 2.79 g of imidazole was uniformly dispersed in 100 ml ofthe solution to obtain a conductive polymer solution. In order toevaluate the π conjugated conductive polymer, the obtained conductivepolymer solution was applied to a glass and dried in a hot air dryingmachine at 120° C. to form a conductive coating having a thickness of 2μm. The electric conductivity of the coating was measured by LORESTA(manufactured by Mitsubishi Chemical Corporation). The results are shownin Table 6.

TABLE 6 Example 27 (Preparation Comparative Comparative Example 6)Example 28 Example 6 Example 7 Electrostatic capacity (μm) 47.5 47.248.1 48.3 Electric conductivity (S/cm) 420 610 3 20 ESR (mΩ) Initial 5 448 35 125° C., after 7 7 579 864 1000 hours

Example 27

An etched aluminum foil (anode foil) was connected to an anode leadterminal and subject to chemical conversion (oxidation) in a solution of10% by weight of ammonium adipate in water to form a dielectric layer onthe aluminum foil surface, by which a capacitor intermediate wasobtained.

The capacitor intermediate and a facing aluminum cathode foil welded toa cathode lead terminal were laminated and rolled up to obtain acapacitor element. A separator was provided between the anode andcathode foils of the capacitor intermediate.

The capacitor element was immersed in the conductive polymer solutionprepared in Preparation Example 6 and then dried in a hot air dryingmachine at 120° C. to form a solid electrolyte layer on the dielectriclayer surface of the capacitor intermediate.

Then, the capacitor element having the solid electrolyte layer and anelectrolyte of 20% by weight of hydrogen ammonium adipate −80% by weightof ethylene glycol were mounted in an aluminum case and the aluminumcase was sealed with a sealing rubber to obtain a capacitor.

The electrostatic capacity at 120 Hz, initial equivalent seriesresistance (ESR) at 100 kHz, ESR at 125° C. and after 1000 hours of theobtained capacitor were measured by LCZ meter 2345 (manufactured by NFCorporation).

Example 28

An etched aluminum foil (anode foil) was connected to an anode leadterminal and subject to chemical conversion (oxidation) in a solution of10% by weight of ammonium adipate in water to form a dielectric layer onthe aluminum foil surface, by which a capacitor intermediate wasobtained.

The capacitor intermediate and a facing aluminum cathode foil welded toa cathode lead terminal were laminated and rolled up to obtain acapacitor element. A separator was provided between the anode andcathode foils of the capacitor intermediate.

The capacitor element was mounted in an aluminum case. A 1:2 mixture ofa solution of 30% by weight of ethylene glycol in pyrrole and a solutionof 20% by weight of ethylene glycol in imidazole was allowed to soak.Then, a solution of 10% by weight of ethylene glycol in ironp-toluenesulfonate was allowed to soak to chemical oxidative polymerizepyrrole. After the polymerization, the capacitor element was rinsed,dried, and sealed with a sealing rubber to obtain a capacitor.

The electrostatic capacity at 120 Hz, initial equivalent seriesresistance (ESR) at 100 kHz, ESR at 125° C. and after 1000 hours of theobtained capacitor were measured.

A 1:2 mixture of a solution of 30% by weight of ethylene glycol inpyrrole and a solution of 20% by weight of ethylene glycol in imidazolewas applied to a glass and a solution of 10% by weight of ethyleneglycol in iron p-toluenesulfonate was dropped thereon to chemicaloxidative polymerize pyrrole. After rinsed and dried, a conductivecoating was formed. The electric conductivity of the conductive coatingwas measured.

The results are shown in Table 6.

Comparative Example 6

A capacitor was obtained in the same manner as in Example 27 except thatthe imidazole was not added in the preparation of the conductive polymersolution of Preparation Example 6.

The electrostatic capacity at 120 Hz, initial equivalent seriesresistance (ESR) at 100 kHz, ESR at 125° C. and after 1000 hours of theobtained capacitor were measured. The results are shown in Table 6.

Comparative Example 7

A capacitor was obtained in the same manner as in Preparation Example 2except that a solution of 20% by weight of ethylene glycol in imidazolewas not added in the preparation of the capacitor of Preparation Example2.

The electrostatic capacity at 120 Hz, initial equivalent seriesresistance (ESR) at 100 kHz, ESR at 125° C. and after 1000 hours of theobtained capacitor were measured. The results are shown in Table 6.

Example 29

A capacitor was obtained and evaluated in the same manner as in Example27 except that 3.85 g of vinylimidazole was used in the conductivepolymer solution obtained in Preparation Example 6 in place ofimidazole. The results are shown in Table 7.

TABLE 7 Example 29 Example 30 Example 31 Example 32 Example 33Electrostatic capacity (μm) 54 67 68 183 194 Electric conductivity(S/cm) 435 412 357 412 453 ESR (mΩ) Initial 5 5 5 10 9 125° C., after 76 7 12 12 1000 hours

Example 30

A capacitor was obtained and evaluated in the same manner as in Example27 except that 3.85 g of vinylimidazole was used in the conductivepolymer solution obtained in Preparation Example 6 in place of imidazoleand 1.4 g of acrylic acid and 0.02 g of ammonium persulfate were added.The results are shown in Table 7.

Example 31

A capacitor was obtained and evaluated in the same manner as in Example27 except that 3.3 g of 1-ethylhydroxyimidazole was used in theconductive polymer solution obtained in Preparation Example 6 in placeof imidazole and 1.4 g of acrylic acid was added. The results are shownin Table 7.

Example 32

An etched aluminum foil (anode foil) was connected to an anode leadterminal and subject to chemical conversion (oxidation) in a solution of10% by weight of ammonium adipate ater to form a dielectric layer on thealuminum foil surface, by which a capacitor intermediate was obtained.

The capacitor intermediate was immersed in the conductive polymersolution prepared in Example 30 and dried in a hot air drying machine at120° C. to form a solid electrolyte layer on the dielectric layersurface of the capacitor intermediate.

Then, a carbon paste was applied to the solid electrolyte layer anddried in a hot air drier at 120° C. A silver paste was further appliedto form a conductive layer, which was dried in a hot air drier at 120°C., by which a cathode was formed.

A lead terminal was connected to the cathode and rolled up to form acapacitor element. A separator was provided between the anode andcathode foils of the capacitor.

Then, the capacitor element having the solid electrolyte layer wasmounted in an aluminum case and sealed with a sealing rubber to form acapacitor. The capacitor was evaluated in the same manner as in Example27. The results are shown in Table 7.

Example 33

An etched aluminum foil (anode foil) was connected to an anode leadterminal and subject to chemical conversion (oxidation) in a solution of10% by weight of ammonium adipate in water to form a dielectric layer onthe aluminum foil surface, by which a capacitor intermediate wasobtained.

Then, a conductive polymer solution was obtained in the same manner asin Example 6 except that 3.85 g of vinylimidazole was used in place ofimidazole and 1.4 g of acrylic acid and 0.01 g of1-[4-(2-hydroxyethoxy)-phenyl]-2-methyl-1-propane-1-on were added. Thecapacitor intermediate was immersed in this solution, dried in a hot airdrier at 120° C. to remove moisture, UV irradiated using a UV irradiatorto form a solid electrolyte layer on the dielectric layer side surfaceof the capacitor.

Then, a carbon paste was applied to the obtained solid electrolyte layerand dried in a hot air drier at 120° C. A silver paste was furtherapplied to form a conductive layer, which was dried in a hot air drierat 120° C., by which a cathode was formed.

A lead terminal was connected to the cathode and rolled up to form acapacitor element. A separator was provided between the anode andcathode foils of the capacitor.

Then, the capacitor element having the solid electrolyte layer wasmounted in an aluminum case and sealed with a sealing rubber to form acapacitor. The capacitor was evaluated in the same manner as in Example27. The results are shown in Table 7.

The capacitors of Examples 27, 28, and 29 to 33, which contains anitrogen-containing aromatic cyclic compound in the solid electrolytelayer of the cathode, had highly conductive cathodes and low equivalentseries resistances. In Example 27, the solid electrolyte layer wassimply formed by applying the conductive polymer solution and drying it.The capacitors of Examples 29 to 33, which contained the cross-linkednitrogen-containing aromatic cyclic compound in the solid electrolytelayer of the cathode, had excellent electrostatic capacities and lowequivalent series resistances.

On the other hand, the capacitors of Comparative Examples 6 and 7, whichdid not contain a nitrogen-containing aromatic cyclic compound in thesolid electrolyte layer of the cathode, had low conductive cathodes andhigh equivalent series resistances.

Preparation Example 7 Synthesis of an Electron AttractiveGroup-Containing Solubilizing Polymer

The amount of 50 g of acrylonitrile and 10 g of styrene were dissolvedin 500 ml of toluene. 1.5 g of azoisobutyronitrile was added as apolymerization initiator. The mixture was allowed to polymerize at 50°C. for 5 hours. Then, a polymer obtained from the polymerization wasrinsed with methanol.

Preparation Example 8 Synthesis of an Anion Group-ContainingSolubilizing Polymer

Sodium ethylsulfonate methacrylate (brand name: Antox, manufactured byNippon Nyukazai Co., Ltd.) was added in the amount of 43.3 g toion-exchanged water (100 ml). A complex oxidant solution of 0.114 g ofammonium persulfate and 0.04 g of iron (II) sulfate previously dissolvedin 10 ml of ion-exchanged water was added to the mixture whilemaintaining at 80° C. and stirring. Then, the mixture was stirred at 80°C. for 3 hours.

After the reaction, the reaction solution was cooled to the roomtemperature. Ion-exchanged water was added in the amount of 1000 ml andthen, 30 g of 50% by weight aqueous sulfuric acid was added. Then, thesolution was concentrated to 300 ml. This operation was repeated fourtimes.

Ion-exchanged water was added in the amount of 2000 ml and the solutionwas concentrated to 300 ml. This operation was until the permeatedsolution was neutralized. The obtained concentrate was dried in an ovento obtain a poly(ethylsulfonate methacrylate).

Preparation Example 9 Synthesis of a Solubilizing Polymer that is aCopolymer of an Anion Group-Containing Component and an ElectronAttractive Group-Containing Component

Sodium ethylsulfonate acrylate in the amount of 40 g and 30 g ofmethacrylonitrile were added to 500 ml of acetonitrile and ion-exchangedwater (7:3). A complex oxidant solution of 0.14 g of ammonium persulfateand 0.04 g of iron (II) sulfate previously dissolved in 10 ml ofion-exchanged water was added to the mixture while maintaining at 80° C.and stirring. Then, the mixture was stirred at 80° C. for 3 hours.

After the reaction, the reaction solution was cooled to the roomtemperature. The amount of 1000 ml of ion-exchanged water was added and,then, 30 g of 50% by weight aqueous sulfuric acid was added. Then, thesolution was concentrated to 300 ml. This operation was repeated fourtimes.

Then, 2000 ml of ion-exchanged water was added and the solution wasconcentrated to 300 ml. This operation was repeated until the permeatedsolution was neutralized. The obtained concentrate was dried in an ovento obtain a copolymer of ethylsulfonate acrylate and methacrylonitrile.

Preparation Example 10 Synthesis of a Solubilizing Polymer that is aCopolymer of an Anion Group-Containing Component and an ElectronAttractive Group-Containing Component

Sodium styrenesulfonate in the amount of 206 g (1 mol) was dissolved ina mixed solvent of 400 g of ion-exchanged water, 100 g of acetonitrile,and 200 g of methanol to obtain a sodium styrenesulfonate solution. 33.5g (0.5 mol) of methacrylonitrile in 100 g of ion-exchanged water, 400 gof acetonitrile, and 100 g of methanol was added to the obtainedsolution, allowed to disperse, and maintained at 80° C.

An oxidant solution of 1.14 g (0.005 mol) of ammonium persulfatepreviously dissolved in 10 ml of water was added dropwise over 20 min.and the solution was stirred for 8 hours.

A polystyrenesulfonic acid-polymethacrylonitrile copolymer was obtainedfrom the sodium polystyrenesulfonate and polymethacrylonitrile copolymersolution obtained in the same manner as in Preparation Example 2.

Preparation of an Antistatic Coating Material Example 34

The amount of 10 g of the solubilizing polymer of Example 7 wasdissolved in 90 g of acetonitrile. The amount of 50 g of3,4-ethylenedioxythiophene and 20 g of sodiumoctadecylnaphthalenesulfonate were added. The mixture was stirred for 1hour while cooling at 10° C.

An oxidant solution of 250 g of iron (II) chloride in 1250 ml ofacetonitrile was added dropwise to the solution over 2 hours whilemaintaining at 10° C. The mixture was further stirred for 12 hours topolymerize 3,4-ethylenedioxythiophene.

After the reaction, 200 ml of methanol was added to the3,4-ethylenedioxythiophene polymer solution, which was then filtered andrinsed to separate the precipitate. The precipitate was dissolved indimethylformamide (DMF) to a concentration of 2% by weight. 100 ml ofthis solution was mixed with 1.1 g of imidazole and stirred to obtain anantistatic coating material.

This antistatic coating material was applied to a PET film having athickness of 25 μm using a comma coater and dried to form an antistaticcoating having a thickness of 0.1 μm. The surface resistance at 10° C.,15% RH was measured by a HIRESTA manufactured by Dia Instruments Co.,Ltd. using MCP-HTP16 as a probe. The total light transmittance (JIS Z8701) and haze (JIS K 6714) were measured. The results are shown inTable 8.

TABLE 8 Comparative Example 34 Example 35 Example 36 Example 37 Example8 Surface resistance (Ω) 2 × 10⁴ 3 × 10⁶ 2 × 10³ 3 × 10⁵ 8 × 10⁷ Totallight 90.1 86.3 90.5 98.5 90.0 transmittance (%) Haze (%) 2.2 3.9 2.50.2 2.1

Example 35

The amount of 10 g of the solubilizing polymer of Example 7 wasdissolved in 90 g of acetonitrile. The amount of 50 g of pyrrole and 20g of p-toluenesulfonic acid were added. The mixture was stirred for 1hour while cooling at −20° C.

An oxidant solution of 250 g of iron (II) chloride in 1250 ml ofacetonitrile was added dropwise to the solution over 2 hours whilemaintaining at −20° C. The mixture was further stirred for 12 hours topolymerize pyrrole.

After the reaction, 2000 ml of methanol was added to the pyrrole polymersolution, which was then filtered and rinsed to separate theprecipitate. The precipitate was dissolved in dimethylformamide (DMF) toa concentration of 2% by weight. 100 ml of this solution was mixed with1.1 g of imidazole and, then, with thermoplastic polyurethane resin andstirred to obtain an antistatic coating material.

The antistatic coating material was evaluated in the same manner as inExample 34. The results are shown in Table 8.

Example 36

The amount of 10 g of the solubilizing polymer of Example 8 wasdissolved in 90 g of water. 50 g of 3,4-ethylenedioxythiophene wasadded. The mixture was stirred for 1 hour while cooling at 5° C.

An oxidant solution of 250 g of iron (II) chloride in 1250 ml of waterwas added dropwise to the solution over 2 hours while maintaining at 5°C. The mixture was further stirred for 12 hours to polymerize3,4-ethylenedioxythiophene.

After the reaction, the mixture was refined by ultrafiltration to removeoxidant residue and unreacted monomers and concentrated to aconcentration of 2% by weight. The amount of 100 ml of the solution wasmixed with 1.1 g of imidazole and stirred to obtain an antistaticcoating material.

The antistatic coating material was evaluated in the same manner as inExample 34. The results are shown in Table 8.

Example 37

The amount of 10 g of the solubilizing polymer of Example 9 wasdissolved in 90 g of water. 50 g of 3,4-ethylenedioxythiophene wasadded. The mixture was stirred for 1 hour while cooling at 0° C.

An oxidant solution of 200 g of ammonium persulfate in 1250 ml of waterwas added in drops to the solution over 2 hours while maintaining at 0°C. The mixture was further stirred for 12 hours to polymerize3,4-ethylenedioxythiophene.

After reaction, the mixture was refined by ultrafiltration to removeoxidant residue and unreacted monomers and concentrated to aconcentration of 2% by weight. The amount of 100 ml of the solution wasmixed with 1.1 g of imidazole and then with allylmethacrylate andfurther with urethane acrylate (manufactured by Negami ChemicalIndustrial Co., Ltd.) as a hard coat component, and stirred to obtain anantistatic coating material.

The antistatic coating material was evaluated in the same manner as inExample 34. The results are shown in Table 8.

Comparative Example 8

The process of Example 34 was repeated except that imidazole was notadded. The evaluation results are shown in Table 8.

Example 38

The amount of 14.2 g (1 mol) of 3,4-ethylenedioxythiophene and asolution of 27.5 g (0.15 mol) of polystyrenesulfonic acid in 2000 ml ofion-exchanged water were mixed at 20° C.

An oxidation catalysis solution of 29.64 g (0.13 mol) of ammoniumpersulfate and 8.0 g (0.02 mol) of iron (II) sulfate in 200 ml ofion-exchanged water was slowly added to the mixed solution whilemaintaining 20° C. and stirring. The mixture was stirred and allowed toreact for 3 hours.

Ion-exchanged water in the amount of 2000 ml of was added to theobtained reaction solution and approximately 2000 ml of the solution wasremoved by ultrafiltration. This operation was repeated three times.

The amount of 200 ml of 10% by weight diluted sulfuric acid and 2000 mlof ion-exchanged water were added to the filtered solution andapproximately 2000 ml of the filtered solution was removed. 2000 ml ofion-exchanged water was added and approximately 2000 ml of the solutionwas removed. This operation was repeated three times.

Then, 2000 ml of ion-exchanged water was added to the obtained filteredsolution and approximately 2000 ml of the filtered solution was removed.This operation was repeated five times. Approximately 1.5% by weight ofblue polystyrenesulfonic acid doped poly(3,4-ethylenedioxythiophene) wasobtained, which was used as a π conjugated conductive polymer solution.

N-vinylimidazole in the amount of 3.16 g was uniformly dispersed in 100ml of the obtained π conjugated conductive polymer solution to obtain anantistatic coating material. The antistatic coating material wasevaluated in the same manner as in Example 34. The results are shown inTable 9.

TABLE 9 Example 38 Example 39 Example 40 Example 41 Example 42 Surfaceresistance (Ω) 7 × 10³ 9 × 10³ 5 × 10³ 2 × 10⁴ 9 × 10³ Total light 97.394.3 95.6 95.4 91.7 transmittance (%) Haze (%) 0.5 0.4 0.7 0.5 1.1

Example 39

An antistatic coating material was obtained by adding 3.83 g of1-(2-hydroxyethyl)-imidazole and 2.18 g of 5-sulfoisophtalic acid in 100ml of the π conjugated conductive polymer solution obtained in Example40 in place of N-vinylimidazole. The antistatic coating material wasevaluated in the same manner as in Example 34. The results are shown inTable 9.

Example 40

An antistatic coating material was obtained by adding 2.0 g of2-hydroxyethylacrylate and 0.01 g of1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-propan-1-on (UVpolymerization initiator) to the antistatic coating material obtained inExample 40.

This antistatic coating material was applied to a PET film having athickness of 25 μm using a comma coater, dried in an oven at 100° C. toremove moisture, and UV irradiated using a UV irradiator to obtain anantistatic coating. The electric properties of the coating wereevaluated in the same manner as in Example 34. The results are shown inTable 9.

Example 41

An antistatic coating material was obtained by adding 3.83 g of1-(2-hydroxyethyl)-imidazole and 1.8 g of polyurethane solution (brandname: REZAMINE D-4080, manufactured by Dainichiseika Color & ChemicalsMfg. Co., Ltd.) to 100 ml of a π conjugated conductive polymer solutionobtained in Example 40 in place of N-vinylimidazole. The antistaticcoating material was evaluated in the same manner as in Example 34. Theresults are shown in Table 9.

Example 42

The amount of 14.2 g (1 mol) of 3,4-ethylenedioxythiophene and asolution of 37.5 g (0.15 mol) of polystyrenesulfonicacid-polymethacrylonitrile copolymer in 2500 ml of ion-exchanged waterwas mixed at 20° C.

An oxidation catalysis solution of 29.64 g (0.13 mol) of ammoniumpersulfate and 8.0 g (0.02 mol) of iron (II) sulfate in 200 ml ofion-exchanged water was slowly added to the mixed solution whilemaintaining 20° C. and stirring. The mixture was stirred and allowed toreact for 4 hours.

Ion-exchanged water in the amount of 3000 ml was added to the obtainedreaction solution and approximately 3000 ml of the solution was removedby ultrafiltration. This operation was repeated three times.

The amount of 200 ml of 10% by weight diluted sulfuric acid and 3000 mlof ion-exchanged water were added to the filtered solution andapproximately 3000 ml of the filtered solution was removed. The amountof 3000 ml of ion-exchanged water was added and approximately 3000 ml ofthe solution was removed. This operation was repeated three times.

Then, 3000 ml of ion-exchanged water was added to the obtained filteredsolution and approximately 3000 ml of the filtered solution was removed.This operation was repeated five times. Approximately 1.5% by weight ofblue polystyrenesulfonic acid doped poly(3,4-ethylenedioxythiophene) wasobtained, which was used as a π conjugated conductive polymer solution.

The amount of 3.83 g of 1-(2-hydroxyethyl)-imidazole and 2.18 g ofsulfoisophthalic acid were uniformly dispersed in 100 ml of the obtainedπ conjugated conductive polymer solution to obtain an antistatic coatingmaterial. The antistatic coating material was evaluated in the samemanner as in Example 34. The results are shown in Table 9.

The antistatic coating materials of Examples 34 to 42, which contained anitrogen-containing aromatic cyclic compound, ensured a transparent andhighly conductive antistatic coating.

On the other hand, the antistatic coating material of ComparativeExample 8, which did not contain a nitrogen-containing aromatic cycliccompound, gave low conductivity.

Example 43 Preparation of an Optical Filter

A PET film having an adhesive layer and a cover film on one surface(film base) was corona treated on the other surface. Then, theantistatic coating material of Example 37 was applied to the coronatreated surface of the PET film. After dried, the surface wasphoto-cured by high pressure mercury lamp to form an antistatic coatingthat also serves as a hard coat layer.

Then, a solution of 80 g of a dispersion of finely porous hollow silicain ethanol (manufactured by Catalysts & Chemicals Industries Co., Ltd.;15.6% by weight of solid components) with 42.0 g of ethanol was appliedto the antistatic coating, dried, and heated at 100° C. for one hour toform an antireflection layer of 90 mm, by which an optical filter wasobtained.

The visible light transmittance, haze, surface resistance, pencilhardness, adhesion of the obtained optical filter were evaluated.

[Visible Light Transmittance, Haze, Surface Resistance]

The visible light transmittance was 86.3%, haze was 1.4%, and surfaceresistance was 3×10⁵Ω.

These were measured in the same manner as for the antistatic coating.

[Pencil Hardness Test]

A hardness that did not cause any damage under a load of 9.8 N wasdetermined using a test pencil specified by JIS S 6006 according to JISK 5400. The obtained pencil hardness was 2H.

[Adhesion Test]

An adhesion test was conducted according to the grid taping method (JISK 5400).

Specifically, 11 each of horizontal and vertical cuts were made atintervals of 1 mm on the antireflection layer side surface of theoptical film (a total of 100 square grids were formed). An adhesive tapewas applied thereon and peeled off. The number of grids in which theoptical filter stayed on the PET film was counted. The result was thatthe optical film stayed in all the 100 grids (100/100).

As a conclusion, this optical filter was sufficiently hard and highlytransparent, antistatic, and adhesive to a base.

Example 44 Production of an Optical Information Recording Medium

A first dielectric layer of 300 nm Ta2O5, an optical recording layer of500 nm Tb—Fe, a second dielectric layer of 300 nm Ta2O5, and a metalreflection layer of 100 nm aluminum were formed on an injection moldedpolycarbonate disc base by sputtering. The antistatic coating materialof Example 37 was applied to the metal reflection layer by a commacoater, dried, and photo-cured by a high pressure mercury lamp to forman antistatic coating that also serves as a hard coat layer, by which anoptical information recording medium was obtained. This opticalinformation recording medium was evaluated as follows.

[Surface Resistance, Pencil Hardness, Adhesion]

The surface resistance, pencil hardness, and adhesion were determined inthe same manner as in Example 45. This optical information recordingmedium had a surface resistance of 3×105Ω and a pencil hardness of theantistatic coating of 2H. The adhesion test showed the antistaticcoating stayed in all the 100 grids.

[Permeability]

The permeability of the antistatic coating for 780 and 635 nm, whichwere the emission wavelengths of the reading laser diode of the opticalinformation recording medium, was measured. The permeability was 98.9%for 780 nm and 98.6% for 635 nm.

As a conclusion, this optical information recording medium was highlytransparent for the wavelengths of 780 and 635 nm, antistatic, anddamage resistant, and adhesive between the antistatic coating and thebase.

The conductive composition of the present invention has applications invarious fields where conductivity is required such as conductive coatingmaterials, antistatic agents, electromagnetic shielding materials,essentially transparent conductive materials, battery materials,conductive adhesive materials, sensors, electronic device materials,semiconductor materials, electrostatic copying materials, photosensitivematerials for printers, transferring bodies, intermediate transferringbodies, shipping materials, and electronic picture materials. Thepresent invention can realizes a capacitor having a highly conductiveand low impedance cathode in a simple manner. The present invention alsorealizes an antistatic coating that is conductive, flexible, and highlyadhesive to a base simply by applying an antistatic coating material.The antistatic coating material yields sufficient antistatic property insmall amounts, therefore reducing production cost. The antistaticcoating material and antistatic coating have applications in variousfields where antistatic property is required such as antistatic films,optical filters, and optical information recording media.

1. A capacitor comprising an anode composed of a porous material ofvalve metal, a dielectric layer formed by oxidizing a surface of theanode, and a cathode provided on the dielectric layer and comprising asolid electrolyte layer containing a π conjugated conductive polymer,which comprises an electron donor compound layer containing an electrondonor element provided between the dielectric layer and the cathode. 2.The capacitor according to claim 1, wherein the electron donor elementof the electron donor compound layer is at least one element selectedfrom the group consisting of nitrogen, oxygen, sulfur, and phosphorus.3. The capacitor according to claim 1, wherein the electron donorcompound of the electron donor compound layer is at least one compoundselected from the group consisting of pyrroles, thiophenes, and furans.4. The capacitor according to claim 1, wherein the electron donorcompound of the electron donor compound layer is amines.
 5. A capacitorcomprising an anode composed of a porous material of valve metal, adielectric layer formed by oxidizing a surface of the anode, and acathode provided on the dielectric layer, wherein the cathode comprisesa solid electrolyte layer containing a π conjugated conductive polymer,a dopant, and a nitrogen-containing aromatic cyclic compound.
 6. Thecapacitor according to claim 5, wherein the cathode further comprises anelectrolytic solution.
 7. The capacitor according to claim 5, whereinthe dopant is a solubilizing polymer containing an anion group.
 8. Thecapacitor according to claim 5, wherein the nitrogen-containing aromaticcyclic compound is substituted or un-substituted imidazoles.
 9. Thecapacitor according to claim 5, wherein the nitrogen-containing aromaticcyclic compound is substituted or un-substituted pyridines.
 10. Thecapacitor according to claim 5, wherein the nitrogen-containing aromaticcyclic compound is cross-linked.